Catalyst Systems For Reforming in Cyclic Flow Reactors

ABSTRACT

Catalyst systems are provided for reforming of hydrocarbons, along with methods for using such catalyst systems. The catalyst systems can be deposited or otherwise coated on a surface or structure, such as a monolith, to achieve improved activity and/or structural stability. The metal oxide support layer can correspond to a thermally stable metal oxide support layer, such as a metal oxide support layer that is thermally phase stable at temperatures of 800° C. to 1600° C. The catalyst systems can be beneficial for use in cyclical reaction environments, such as reverse flow reactors or other types of reactors that are operated using flows in opposing directions and different times within a reaction cycle.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and the benefit of U.S. Provisional Application No. 63/090,880, filed on Oct. 13, 2020, the disclosure of which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

This invention relates to compositions suitable for use in hydrocarbon reforming in high temperature environments.

BACKGROUND OF THE INVENTION

Reverse flow reactors are an example of a reactor type that is beneficial for use in processes with cyclic reaction conditions. For example, due to the endothermic nature of reforming reactions, additional heat needs to be introduced on a consistent basis into the reforming reaction environment. Reverse flow reactors can provide an efficient way to introduce heat into the reaction environment. After a portion of the reaction cycle used for reforming or another endothermic reaction, a second portion of the reaction cycle can be used for combustion or another exothermic reaction to add heat to the reaction environment in preparation for the next reforming step. U.S. Pat. Nos. 7,815,873 and 8,754,276 provide examples of using reverse flow reactors to perform various endothermic processes in a cyclic reaction environment.

Endothermic reactions such as reforming can also benefit from having a substantial amount of available catalytic surface area. Ceramic monolith structures are an example of a type of structure that can provide a high available surface area. One option can be to use a monolith corresponding to a packed array of cells or channels that the reactant gases pass through. Washcoats are added to such monoliths to provide catalytic activity.

U.S. Patent Application Publication 2020/0030778 describes monolith structures for use in hydrocarbon reforming where the monolith structures are composed of a mixture of one or more dopant metal oxides and one or more structural oxides. The dopant metal(s) and structural oxide(s) are selected based on the relative Gibbs free energy values for the dopant metal oxide and the structural oxide. NiO and Al₂O₃ are described as an example of a suitable combination of a dopant metal oxide and a structural oxide for forming a monolith structure.

SUMMARY OF THE INVENTION

In various aspects, a hydrocarbon reforming catalyst system and support structure is provided. The catalyst system includes a catalyst having reforming activity. The catalyst system further includes a metal oxide support layer that is thermally phase stable at 800° C. to 1600° C. comprising stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, a corundum group oxide, or a combination thereof. The catalyst and the metal oxide support layer can correspond to a catalyst system supported by one or more surfaces of the support structure. The catalyst system can correspond to 0.5 wt % or more of a combined weight of the catalyst system and the support structure.

In another aspect, a method for forming a catalyst system is provided. The method includes forming a catalyst system comprising a catalyst and a metal oxide support layer that is thermally phase stable at 800° C. to 1600° C. The catalyst can have reforming activity and can include Ni, Rh, Ru, Pd, Pt, Cu, Ir, or a combination thereof. The metal oxide support layer can include stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, a corundum group oxide, or a combination thereof. The method further includes supporting the catalyst system on one or more surfaces of a support structure. The method further includes annealing the supported catalyst system and the support structure at an annealing temperature of 1000° C. or more to form an annealed catalyst system and support structure. Additionally, the method includes exposing the annealed catalyst system and support structure to cyclic reforming conditions comprising a peak temperature of 1000° C. or more in the presence of a hydrocarbon feed to form H₂. The cyclic reforming conditions can include a reforming step and a regeneration step. Optionally, the annealing temperature can be greater than the peak temperature.

In another aspect, a method for reforming hydrocarbons in a cyclic reaction environment is provided. The method includes reacting a mixture comprising fuel and 0.1 vol % or more of O₂ under combustion conditions in a combustion zone within a reactor to heat one or more surfaces in a reaction zone to a regenerated surface temperature of 1000° C. or more. The 0.1 vol % or more of O₂ can include 120% or more of a stoichiometric molar amount of O₂ for combustion of the fuel. The reaction zone can include a catalyst system supported on one or more surfaces of a support structure. The method further includes exposing a reactant stream including a reformable hydrocarbon to the one or more surfaces in the reaction zone to increase the temperature of the reactant stream. Additionally, the method includes exposing the reactant stream to the catalyst system in the reaction zone at a temperature of 1000° C. or more to form a product stream containing H₂. A direction of flow for the reactant stream within the reaction zone can be reversed relative to a direction of flow for the mixture. The catalyst system can include a catalyst and a metal oxide support layer, the catalyst having reforming activity and comprising Ni, Rh, Ru, Pd, Pt, Cu, Ir, or a combination thereof, the metal oxide support layer including stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, a corundum group oxide, or a combination thereof. The metal oxide support layer can optionally be thermally phase stable at 800° C. to 1600° C.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an example of operation of a reverse flow reactor. FIG. 1A shows the reforming step of a reforming reaction. FIG. 1B shows a regeneration step of a reforming reaction.

FIG. 2 shows an example of a reverse flow reactor.

FIG. 3 shows an example of a catalyst system deposited on surfaces of a honeycomb monolith.

FIG. 4 shows an example of a temperature profile for performing steam reforming within a reverse flow reactor.

FIG. 5 shows an SEM image of an NiAl₂O₄ catalyst system washcoated on a monolith after exposure to cyclic reforming conditions.

FIG. 6 shows SEM images of an Rh₂O₃/α-Al₂O₃ catalyst system washcoated on a monolith after exposure to cyclic reforming conditions for 750 hours.

FIG. 7 shows conversion of methane during reforming under cyclic reforming conditions in the presence of various catalyst systems.

FIG. 8 shows another SEM image of the surface of an NiAl₂O₄ catalyst system after exposure to cyclic reforming conditions.

FIG. 9 shows conversion of methane during reforming under cyclic reforming conditions in the presence of various catalyst systems.

FIG. 10 shows conversion of methane during reforming under cyclic reforming conditions in the presence of a catalyst system supported on a monolith composed of NiAl₂O₄.

DETAILED DESCRIPTION OF THE EMBODIMENTS

All numerical values within the detailed description and the claims herein are modified by “about” or “approximately” the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

Overview

In various aspects, catalyst systems are provided for reforming of hydrocarbons, along with methods for using such catalyst systems. The catalyst systems can be deposited or otherwise coated on a surface or structure, such as a monolith, to achieve improved activity and/or structural stability. In this discussion, a catalyst system is defined to include at least one catalyst corresponding to one or more catalytic metals, optionally in the form of a metal oxide, and at least one metal oxide support layer. In some aspects, the catalyst and metal oxide support layer can be coated on the monolith at the same time, such as in the form of a washcoat layer on the support. In such aspects, the catalyst can be intermixed with the metal oxide support layer. Alternatively, the catalyst and metal oxide support layer can be deposited sequentially so that the support layer is deposited first, followed by the catalyst. In some aspects, the metal oxide support layer can correspond to a thermally stable metal oxide support layer, such as a metal oxide support layer that is thermally phase stable at temperatures of 800° C. to 1600° C. Optionally, an intermediate bonding layer can be applied to at least a portion of the monolith or other structure prior to depositing the catalyst system. The catalyst systems can be beneficial for use in cyclical reaction environments, such as reverse flow reactors or other types of reactors that are operated using flows in opposing directions and different times within a reaction cycle. The reaction conditions in cyclical reaction environments can also undergo swings in temperature and/or pressure during a reaction cycle.

In order to use a catalyst system in a cyclic reaction environment, the catalyst system can typically be coated or otherwise supported on a structure or surface that will be present within the reaction environment during the reforming process cycle. For example, the catalyst system can be applied as a washcoat on the surface of one or more monoliths or other structures that are placed in the reactor. Such a monolith or other structure can include a large number of channels or cells per unit surface area, in order to substantially increase the amount of structural surface area that can be coated with the catalyst system. In some aspects, the catalyst system can be deposited on a monolith or other structure that is composed of a low surface area material that is phase stable under high temperature reforming conditions. In such aspects, the catalyst system and monolith or other structure can be annealed at temperatures at or above the processing temperatures prior to use. This can provide further structural stability for the catalyst system, resulting in an unexpected increase in the amount of time the catalyst system can substantially retain the desired level of reforming activity.

FIG. 3 shows an example of a portion of a monolith 300 that includes a catalyst system 310 deposited (or otherwise coated) on the surfaces of the monolith 300. In the example shown in FIG. 3, the portion of the monolith corresponds to a regular pattern of square cells that allow reactant gases (such as a reforming feed gas flow) to pass through the cells. In other aspects, any convenient type of cell shape can be used, such as round or hexagonal cells. The catalyst system 310 corresponds to a layer that includes catalyst 312 and a metal oxide support 314 that is coated on the surfaces of the cells of the monolith.

In some aspects, at least one catalyst in the catalyst system can correspond to a catalyst that includes Ni. NiAl₂O₄ is an example of a catalyst system that can initially correspond to Ni (or NiO when oxidized) as a catalyst and Al₂O₃ as the metal oxide support layer. During exposure to the cyclic reforming conditions, at least a portion of the NiO and Al₂O₃ can combine to form a spinel phase structure corresponding to NiAl₂O₄. Another example of a catalyst system that includes Ni in the catalyst can correspond to NiO as the catalyst and yttrium-stabilized zirconia (YSZ) as the metal oxide support. Still another example of a catalyst system that includes Ni in the catalyst can correspond to NiO as the catalyst and a perovskite oxide as the metal oxide support.

Optionally, still further benefits can be achieved by using the catalyst systems in conjunction with using a reaction cycle that includes a modified regeneration or heat incorporation step. In such optional aspects, the modified regeneration step can include additional oxygen so that the catalyst system is in a more highly oxidized state during the next reforming step.

In some aspects, the catalyst system can correspond to one or more catalysts in a single zone. In other aspects, the catalyst system can correspond to a plurality of catalyst zones. Optionally in such aspects, at least one catalyst zone can include a catalyst that is different from the catalyst(s) in a second catalyst zone.

Reforming of hydrocarbons to form synthesis gas is a potentially desirable pathway for reducing or minimizing CO₂ emissions associated with hydrocarbon fuels. Reforming can convert hydrocarbon fuels into H₂, a fuel with no CO₂ emissions, and CO or CO₂. By separating the H₂ from the carbon oxides in a single location, some of the difficulties associated with preventing CO₂ emissions can be reduced or minimized. However, due to the elevated temperatures required for hydrocarbon reforming, balancing efficient reforming of hydrocarbons with energy consumption and operating lifetime for equipment remains a challenge.

One option for improving the energy efficiency of a reforming process can be to use a reaction system such as a reverse flow reactor, or another type of reaction system where flows are passed through the reactor in opposing directions during reforming steps and regeneration (heating) steps. Reverse flow reactors (and other similar types of reactors) can provide several types of advantages. First, by using multiple steps with different flows during a reaction cycle, heat can be added to the reaction zone where reforming will occur by performing combustion in or near the reaction zone. This can reduce or minimize heat loss while attempting to add heat to the reaction zone. Use of flows in opposing directions can provide further benefits with regard to developing a desirable temperature profile within the reaction zone. Reverse flow reactors will be used herein as an example of this type of system, but it is understood that reverse flow reactors are an example of a reactor that can provide such benefits.

While reverse flow reactors can provide a variety of benefits, maintaining a desirable operating lifetime can present challenges. Due to the high temperatures that are introduced into a reverse flow reactor for reforming, breakdown of materials can occur. In particular, the cyclic high temperature environment, including both reducing and oxidizing conditions, can pose problems for catalyst systems. In various aspects, catalyst systems are provided that can provide desirable catalytic activity for reforming and that can maintain that desirable activity for extended time periods in the presence of a reaction environment with cyclic oxidizing and reducing conditions at elevated temperature.

High Temperature Reforming Catalyst System—NiAl₂O₄ and NiO/NiAl₂O₄

In some aspects, the catalyst system can correspond to a mixture of NiO and Al₂O₃. Under the cyclic high temperature reforming conditions, the NiO and the Al₂O₃ in the will react to form a mixed phase of NiO, NiAl₂O₄, and/or Al₂O₃. Additionally, based on cyclic exposure to oxidizing and reducing conditions, the catalyst can be converted from a substantially fully oxidized state, such as a combination of oxides including NiO, NiAl₂O₄ and Al₂O₃, to various states including at least some Ni metal supported on a surface. In this discussion, a catalyst system that includes both NiO and Al₂O₃ is referred to as an NiAl₂O₄ catalyst system.

Based on the stoichiometry for combining NiO and Al₂O₃ to form NiAl₂O₄, a catalyst including a molar ratio of Al to Ni of roughly 2.0 (i.e., a ratio of 2:1) could result in formation of NiAl₂O₄ with no remaining excess of NiO or Al₂O₃. Thus, one option for forming an NiAl₂O₄ catalyst is to combine NiO and Al₂O₃ to provide a stoichiometric molar ratio of Al to Ni of roughly 2.0. In some other aspects, an excess of NiO can be included in the catalyst relative to the amount of alumina in the support, so that at least some NiO is present in a fully oxidized state. In such aspects, the molar ratio of Al to Ni in the catalyst can be less than 2.0. For example, the molar ratio of Al to Ni in a NiO/NiAl₂O₄ catalyst can be 0.1 to 2.0, or 0.1 to 1.9, or 0.1 to 1.5, or 0.5 to 2.0, or 0.5 to 1.9, or 0.5 to 1.5, or 1.0 to 2.0, or 1.0 to 1.9, or 1.2 to 1.5, or 1.5 to 2.0, or 1.5 to 1.9. In still other aspects, an excess of Al₂O₃ can be included in the catalyst relative to the amount of Ni, so that at least some Al₂O₃ is present in a fully oxidized state. In such aspects, the molar ratio of Al to Ni in the catalyst can be greater than 2.0. For example, the molar ratio of Al to Ni in a NiAl₂O₄/Al₂O₃ catalyst can be 2.0 to 10, or 2.1 to 10, or 2.0 to 5.0, or 2.1 to 5.0, or 2.0 to 4.0, or 2.1 to 4.0.

In various aspects, an NiAl₂O₄ catalyst can be incorporated, for example, into a washcoat that is then applied to a surface or structure within a reactor, such as a monolith. By providing NiO and Al₂O₃ as a catalyst system that is then deposited on a separate monolith (which can then form NiAl₂O₄ under the cyclic conditions), the activity of the catalyst can be maintained for unexpectedly longer times relative to using a monolith that directly incorporates NiO and Al₂O₃ into the monolith structure.

When a composition is formed that includes both nickel oxide and alumina, the NiO and Al₂O₃ can react to form a compound corresponding to NiAl₂O₄. However, when NiO (optionally in the form of NiAl₂O₄) is exposed to reducing conditions, the divalent Ni can be reduced to form metallic Ni. Thus, under cyclic reforming conditions that include both high temperature oxidizing and reforming environments, at least a portion of NiAl₂O₄ catalyst can undergo cyclic transitions between states corresponding to Ni metal and Al₂O₃ and NiAl₂O₄. It is believed that this cyclic transition between states can allow an NiAl₂O₄ catalyst to provide unexpectedly improved activity over extended periods of time. Without being bound by any particular theory, it is believed that at least part of this improved activity for extended time periods is due to the ability of Ni to “re-disperse” during the successive oxidation cycles. It is believed this re-dispersion occurs in part due to the formation of NiAl₂O₄ from NiO and Al₂O₃. Catalyst sintering is a phenomenon known for many types of catalysts where exposure to reducing conditions at elevated temperature can cause catalyst to agglomerate on a surface. Thus, even if the surface area of the underlying surface remains high, the agglomeration of the catalyst may reduce the amount of available catalyst active sites, as the catalyst sinters and forms lower surface area deposits on the underlying surface. By contrast, it is believed that the cyclic transition between states can allow the Ni in an NiAl₂O₄ catalyst system to retain good dispersion, so that catalyst activity can be maintained. It is believed that further advantage can be obtained by using a sufficient amount of excess oxygen during the regeneration step so that all available Ni is oxidized back to NiO and/or NiAl₂O₄.

It is noted that by supplying both NiO as a catalyst and Al₂O₃ as a metal oxide support layer as part of the catalyst system, the alumina for forming NiAl₂O₄ is already provided as part of the catalyst system. It is believed that this reduces or minimizes interaction of Ni with any alumina that may be present in the monolith composition, and therefore reduces or minimizes degradation of the underlying monolith when exposed to successive cycles of high temperature oxidation and reduction.

Although NiAl₂O₄ could potentially be used as a structural material for forming a monolith, it has been unexpectedly found that using NiAl₂O₄ as a washcoat for a separate structure (such as a monolith) can allow catalytic activity to be maintained for substantially longer time periods. It is noted that U.S. Patent Application Publication 2020/0030778 describes using a monolith composed of a combination of NiO and Al₂O₃ as a structure to provide reforming catalytic activity under cyclic high temperature reforming conditions. However, it is believed that the cyclic transition of states for a monolith composed at least partially of NiAl₂O₄ can contribute to structural breakdown of the monolith. Because a monolith structure typically includes a large number of cells or passages per unit area, the structural breakdown of the monolith can result in filling or even collapse of the cells, so that the available surface area that the reactant gas flows are exposed to in the reforming environment is greatly reduced.

In some aspects, NiAl₂O₄ can be used as a catalyst system when a single catalyst zone is used in a reforming reactor. In some aspects where multiple catalyst zones are present, NiAl₂O₄ can be used as a catalyst system in the highest temperature zone, in an intermediate temperature zone, or a combination thereof.

Other Catalyst Systems Containing Ni

NiO supported on yttria-stabilized zirconia (NiO/YSZ) is another example of an Ni-containing catalyst system that can be used for reforming. Although α-Al₂O₃ is phase stable, it is able to react with NiO at high temperature to form NiAl₂O₄. It is believed, however, that YSZ does not react with Ni (NiO) at high temperatures. Thus, it is believed that in the NiO/YSZ system, a cyclic oxidation and reduction of Ni to NiO and back to Ni metal does occur, but redispersion does not occur. However, NiO/YSZ can still provide stable reforming activity in a cyclic high temperature reforming environment. In some aspects, to assist with bonding of NiO/YSZ to a monolith, an intermediate oxide layer of α-Al₂O₃ can first be deposited as a washcoat on the monolith. The NiO/YSZ layer can then be deposited on the intermediate oxide layer.

NiO/YSZ represents an alternative type of catalyst system, as YSZ is a phase stable support that does not react with Ni to form a different material. In order to determine stability of the support oxide layer, a first sample of NiO/YSZ was exposed to calcining at 1300° C., while a second sample was steamed in air at 1000° C. X-ray diffraction was used to verify that no phase changes occurred. However, based on Brunauer-Emmett-Teller (BET) surface area analysis, it was observed that the surface area of the NiO/YSZ sample was roughly 53 m²/g prior to the calcining and steaming, and roughly 5 m²/g after the calcining and steaming.

Still another example of a catalyst system containing Ni can be NiO on a perovskite oxide, such as Sr_(0.65)La_(0.35)TiO₃ (SLT).

Reforming Catalyst and Metal Oxide Support Layer—General

In various aspects, one option for adding a reforming catalyst to a monolith can be to coat the monolith with a mixture of a catalyst (optionally in oxide form) and metal oxide support layer. For example, powders of the catalyst oxide and the metal oxide support layer can be used to form a washcoat that is then applied to the monolith (or other structure). This can result in a catalyst system where the catalyst is mixed within/distributed throughout the metal oxide support layer, as opposed to the catalyst being deposited on top of the metal oxide support layer. In other words, at least a portion of the catalyst system can correspond to a mixture of the catalyst and the support layer. In other aspects, any convenient method for depositing or otherwise coating the catalyst system on the monolith or other structure can be used. The weight of the catalyst system on the monolith (or other structure) can correspond to 0.1 wt % to 10 wt % of the total weight of the catalyst system plus monolith, or 0.5 wt % to 10 wt %, or 2.0 wt % to 10 wt %, or 0.1 wt % to 6.0 wt %, or 0.5 wt % to 6.0 wt %, or 2.0 wt % to 6.0 wt %.

In some aspects, the catalyst system can include a thermally stable metal oxide support layer. A thermally stable metal oxide support layer corresponds to a metal oxide that is thermally phase stable with regard to structural phase changes at temperatures between 800° C. to 1600° C. In some aspects, such a thermally stable metal oxide support layer can be formed by coating a surface (such using a washcoat) with a metal oxide powder that has a surface area of 20 m²/g or less. For example, the metal oxide powder used for forming a thermally stable metal oxide coating can have a surface area of 0.5 m²/g to 20 m²/g, or 1.0 m²/g to 20 m²/g, or 5.0 m²/g to 20 m²/g. High temperature reforming refers to reforming that takes place at a reforming temperature of 1000° C. or more, or 1100° C. or more, or 1200° C. or more, such as up to 1500° C. or possibly still higher. In various aspects, a catalyst can be annealed at a temperature of 1000° C. or more, or 1100° C. or more, or 1200° C. or more, or 1300° C. or more, such as up to 1600° C. or possibly still higher. This temperature can be substantially similar to or greater than the peak temperature the catalyst is exposed to during a reforming process cycle. An annealing temperature that is substantially similar to a peak temperature can correspond to an annealing temperature that differs from the peak temperature by 0° C. to 50° C.

As an example of a thermally stable metal oxide support layer, alumina has a variety of phases, including α-Al₂O₃, γ-Al₂O₃, and θ-Al₂O₃. A metal powder of α-Al₂O₃ can typically have a surface area of 20 m²/g or less. By contrast, the γ-Al₂O₃ and θ-Al₂O₃ phases have higher surface areas, and a metal powder for use in a washcoat solution of γ-Al₂O₃ and/or θ-Al₂O₃ will have a surface area of greater than 20 m²/g. It is conventionally believed that phases such as θ-alumina or γ-alumina are superior as a supporting structure for a deposited catalyst, as the greater surface per gram of θ-alumina or γ-alumina will allow for availability of more catalyst active sites than α-alumina. However, phases such as γ-Al₂O₃ and θ-Al₂O₃ are not thermally phase stable at temperatures of 800° C. to 1600° C. At such high temperatures, phases such as γ-Al₂O₃ and θ-Al₂O₃ will undergo phase transitions to higher stability phases. For example, at elevated temperatures, γ-Al₂O₃ will first convert to Δ-Al₂O₃ at roughly 750° C.; then Δ-Al₂O₃ will convert to θ-Al₂O₃ at roughly 950° C.; then θ-Al₂O₃ will then convert to α-Al₂O₃ with further exposure to elevated temperatures between 1000° C. and 1100° C. Thus, α-Al₂O₃ is the thermally phase stable version of Al₂O₃ at temperatures of 800° C. to 1600° C.

Without being bound by any particular theory, it is believed that such phase changes during exposure to elevated temperature can contribute to degradation of the catalyst and/or the structure supporting the catalyst. By contrast, by using a support that is phase stable at an elevated annealing temperature and then annealing the catalyst (including support) at the elevated annealing temperature, the resulting catalyst can substantially maintain an initial catalytic activity level for an extended period of time. It is noted that the initial catalytic activity achieved by depositing catalyst on a monolith formed from a phase stable, low surface area per gram material may be lower than depositing catalyst on a similar monolith formed from a material having a higher surface area per gram. However, it has been discovered this initial activity advantage for the higher surface area material is quickly lost during exposure to cyclic high temperature reforming conditions.

As a further illustration, without being bound by any particular theory, γ-Al₂O₃ is a transitional alumina that may be viewed as a defect oxyhydroxide, with a spinel related crystalline structure. In prior academic work, γ-Al₂O₃ has been formulated an alumina spinel, with defect sites having a formula of Al_(8/3)□_(1/3)O₄, where □ symbolizes open cation sites. Including the hydroxyls, it may be viewed as Al_(2.5)□_(0.5)O_(3.5)(OH)_(0.5). Such γ-Al₂O₃ is thermally unstable with respect to α-Al₂O₃. Although θ-Al₂O₃ is more crystalline and has less surface area and hydroxide content compared to γ-Al₂O₃, θ-Al₂O₃ also includes defect sites (i.e., open cation sites, and is also thermally unstable relative to α—Al₂O₃. Thus, γ- and θ-Al₂O₃ both have defect sites (□) capable of reacting with multivalent cations (or metal oxides). Both Rh(O) and Ni(O) may react to produce denser phases, where Rh and Ni may not be as chemically accessible for catalytic reaction as compared to their oxide or metallic states. Even in the absence of reactions with Rh or Ni, γ- and θ-Al₂O₃ are thermodynamically unstable with respect to α—Al₂O₃ under high temperature conditions.

It has been discovered that using a thermally stable metal oxide in a catalyst system, in combination with annealing of the catalyst system on the monolith at high temperature, can provide unexpected activity benefits and structural stability benefits over extended periods of time. Without being bound by any particular theory, when a catalyst system including a non-thermally stable metal oxide is used in a coating for a monolith, exposing such a catalyst system to a cyclic high temperature reforming environment can result in structural degradation of the catalyst system. It is believed that this structural degradation of a catalyst system can contribute to a reduction in available catalyst sites, possibly due to the catalyst becoming buried within a degraded structure and/or additional sintering or agglomeration of the catalyst as the non-thermally stable metal oxide in the catalyst system converts to a lower surface area phase. This structural degradation can be observed, for example, by examining the catalyst system on a monolith after exposure to a cyclic high temperature reaction environment. For a conventional catalyst system, after exposure to a cyclic high temperature reaction environment, the catalyst system can be readily scraped off of the underlying structure. Additionally, a substantial reduction in activity can be observed.

By contrast, when a catalyst system is used that includes a thermally stable metal oxide, the activity of the catalyst in the catalyst system can be unexpectedly maintained for extended run lengths with little or no loss of activity. Additionally, after exposure to a cyclic high temperature reforming environment, the catalyst system can unexpectedly remain strongly adhered or coated on the underlying monolith or other structure. It is noted that the initial catalyst activity may be lower than for a conventional system, since thermally stable metal oxides typically have a relatively low surface area. This is believed to initially reduce the number of available catalytic sites. However, because the thermally stable metal oxide does not undergo phase transitions when exposed to heat, the catalytic activity of a catalyst system including a thermally stable metal oxide can be maintained. Due to the rapid deactivation for a conventional catalyst or catalyst system, the activity of a conventional catalyst system can rapidly fall below the activity of a catalyst system using a thermally stable metal oxide.

Additionally, further improvements can be achieved by annealing the catalyst system and the underlying monolith (or other supporting structure) at temperatures that are substantially the same as or greater than the peak temperatures the supporting structure is exposed to during the reforming process.

One of the distinctions between using a catalyst system including a thermally stable metal oxide and a catalyst system that does not use a thermally stable oxide is that the catalyst system including the thermal stable metal oxide can have improved adhesion to the underlying support structure after exposure to the cyclic high temperature reforming environment.

Adhesion of the washcoat after operation can be quantified by the amount of force needed to de-adhere the washcoat. In prior operation, washcoats comprised of theta and gamma alumina were de-adhered with minimal force, such as an amount of force similar to a paint brush stroke (weak). In operation with the phase stable supports, the force needed to de-adhere the washcoat was high, similar to the scraping of dried epoxy off of a glass surface (strong). Due to these differences, only small amounts of washcoat could be de-adhered from the phase stable materials, whereas large amounts of washcoat could be de-adhered from the gamma and theta supports.

Other methods for evaluating adhesion of the washcoat include, but are not limited to, (i) a thermal cycling method, (ii) a mechanical attrition method, and (iii) an air-knife method. As a non-limiting example, the thermal cycling method can be performed by heating the washcoated materials to high temperatures in the range of 800 to 1300° C., cooling the heated substrates to ambient temperature, and repeating such a cycle at least five times. As another non-limiting example, the mechanical attrition method can be performed by placing the washcoated materials inside a plastic container and shaking the container on a vibration table for at least 30 minutes.

Adhesion of the washcoated materials can be determined based on exposing a washcoated structure to thermal cycling conditions and then measuring the de-adhered material before and after mechanical attrition testing by mass change. Prior to thermal cycling, the weight of the washcoat on the support structure can be determined. The washcoated structure can then be exposed to thermal cycling conditions. The thermal cycling conditions can correspond to the thermal cycling method above, or the washcoated structure can be exposed to cyclic high temperature reforming conditions for at least five reforming cycles. A catalyst system including a thermally phase stable support can provide good adhesion after mechanical attrition testing, corresponding to retaining 80 wt % or more of the initial washcoat, or retaining 90 wt % or more of the initial washcoat, or 95 wt % or more of the initial washcoat. By contrast, a catalyst system not including a thermally phase stable support that is exposed to cyclic high temperature conditions and then exposed to mechanical attrition testing can retain 75 wt % or less of the initial washcoat.

A catalyst system can be applied to a monolith or other structure, for example, by applying the catalyst system as a washcoat suspension. To form a washcoat suspension, the catalyst system can be added to water to form an aqueous suspension having 10 wt % to 50 wt % solids. For example, the aqueous suspension can include 10 wt % to 50 wt % solids, or 15 wt % to 40 wt %, or 10 wt % to 30 wt %. Optionally, an acid or a base can be added to the aqueous suspension to reduce or raise, respectively, the pH so as to change the particle size distribution of the alumina catalyst and/or binder particles. For example, acetic acid or another organic acid can be added to achieve a pH of 3 to 4. The suspension can then be ball milled (or processed in another manner) to achieve a desired particle size for the catalyst particles, such as a particle size of 0.5 μm to 5 μm. After milling, the suspension can be stirred until time for use so that the particles are distributed substantially uniformly in the solution.

The washcoat suspension can then be applied to a monolith structure to achieve a desired amount of catalyst (such as nickel or rhodium) on the monolith surface. As an example, in one aspect a washcoat thickness of 10 microns was achieved by forming a washcoat corresponding to 10 wt % of the monolith structure. Any convenient type of monolith structure can be used to provide a substantial surface area for support of the catalyst particles. The washcoat can be applied to the monolith to form cells having inner surfaces coated with the catalyst. One option for applying the washcoat can be to dip or otherwise submerge the monolith in the washcoat suspension.

After clearing the cell channels of excess washcoat, the catalyst system coated on the monolith can be optionally dried. Drying can correspond to heating at 100° C. to 200° C. for 0.5 hours to 24 hours. After any optional drying, calcination can be performed. In some aspects, calcining can correspond to heating at 200° C. to 800° C. for 0.5 hours to 24 hours.

In other aspects, a high temperature calcination step can be used, so that the calcining temperature for the catalyst system coated on the monolith is substantially similar to or greater than the peak temperature the monolith will be exposed to during the cyclic high temperature reforming reaction. For a monolith in a high temperature zone, this can correspond to calcining the catalyst system coated on the monolith at a temperature of 800° C. or more, or 1000° C. or more, or 1200° C. or more, or 1300° C. or more, such as up to 1600° C. or possibly still higher. It is noted that if multiple catalyst zones are present, the calcination for monoliths in different catalyst zones can be different.

It has been unexpectedly discovered that performing calcination at a temperature similar to or greater than the peak temperature during the cyclic high temperature reforming process can unexpectedly allow for improved activity for the catalyst system and/or adhesion of the catalyst system to the underlying monolith. Without being bound by any particular theory, it is believed that exposing the monolith and deposited catalyst system to elevated temperatures prior to exposure of the catalyst to a cyclic reaction environment can facilitate forming a stable interface between the catalyst system and the monolith. This stable interface can then have improved resistance to the high temperature oxidizing and/or reducing environment during the reforming process, resulting in improved stability for maintaining the catalyst system on the surface of the monolith.

In various aspects, suitable catalytic metals can include, but are not limited to, Ni, Co, Fe, Pd, Rh, Ru, Pt, Ir, Cu, Ag, Au, Zr, Cr, Ti, V, Mo, Nb, and combinations thereof. The catalytic metal can be selected based on the desired type of catalytic activity. Such catalytic metals may be used in a catalyst in the form of a metal oxide. In some aspects, for reforming of hydrocarbons in the presence of H₂O and/or CO₂ to make hydrogen, Ni, Rh, Ru, Pd, Pt, Ir, Cu, Co, or a combination of thereof can be suitable catalytic metals. The weight of catalytic metal oxide in the catalyst system can range from 0.1 wt % to 70 wt %, or 1.0 wt % to 60 wt %, or 2.0 wt % to 50 wt %, relative to the total weight of the catalyst system. In some aspects where the catalytic metal corresponds to a precious metal or noble metal, the weight of catalytic metal oxide in the catalyst system can range from 0.1 wt % to 10 wt %, or 0.2 wt % to 7.0 wt %, or 0.5 wt % to 4 wt %.

The catalytic metals can be selected to provide long term stable performance at specific temperature zones of the catalytic bed. This can allow for steady methane conversion, phase stability with the metal oxide support, and reduced or minimized sintering of catalytic metals. As an example involving three catalyst zones, the catalyst system in a highest temperature catalytic zone (e.g. 800˜1250° C.), which is exposed to some of highest temperatures and most severe temperature swings, can be composed of Ni as a catalytic metal (NiO as a catalytic metal oxide) and Al₂O₃ as a metal oxide support. It is noted that this catalyst system can at least partially convert to NiAl₂O₄ during portions of the cyclic reforming process. This catalyst system can be formed, for example, by using a mixture of NiO and Al₂O₃, as a washcoat on α-Al₂O₃ monoliths. In such an example, a catalyst system in a medium temperature catalytic zone (e.g. 600˜1150° C.) can be composed of Ni and Rh as catalytic metals (NiO and Rh₂O₃ as catalytic metal oxide), and Al₂O₃ as a metal oxide support. To form this catalyst system, a mixture of NiO and Rh₂O₃, as the catalytic material and Al₂O₃ (optionally but preferably α-Al₂O₃) as a metal oxide support material can be washcoated on a monolith comprising of 95 wt % α-Al₂O₃, 4 wt % SiO₂ and 1 wt % TiO₂. In such an example, a catalyst system in a low temperature catalytic zone (e.g. 400˜1050° C.) can be composed of Rh as catalytic metal (Rh₂O₃ as catalytic metal oxide) and α-Al₂O₃ as a metal oxide support. To form this catalyst system, a mixture of Rh₂O₃ and α-Al₂O₃ as the catalytic material can be washcoated on a monolith comprising 93 wt % α-Al₂O₃, 5 wt % SiO₂ and 2 wt % MgO.

In various aspects, suitable metals for the metal oxide support layer in the catalyst system can include, but are not limited to, Al, Si, Mg, Ca, Sr, Ba, K, Na, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ni, Co, Y, La, Ce, and combinations thereof. The metal (or metals) for the metal oxide support can be selected so that the metal oxide support substantially does not convert to metallic form under the reducing conditions present in the cyclic reaction environment. As an example, when the catalytic metal oxide is NiO, one option for a metal oxide support is Al₂O₃, preferably α-Al₂O₃. Another example of a suitable metal oxide support, optionally, in combination with NiO as the catalytic metal oxide, is a mixture of Al₂O₃ with SiO₂, MgO and/or TiO₂. In such an example, SiO₂ can combine with Al₂O₃ to form a mullite phase that could increase resistance to thermal shock and/or mechanical failure. Additionally or alternately, in such an example, MgO and/or TiO₂ can be added. The weight of metal oxide support in the catalyst bed can range from 1.0 wt % to 40 wt %, or 2.0 wt % to 30 wt %, or 3.0 wt % to 20 wt %, relative to the total weight of the monolith in the catalyst bed.

In various aspects, a metal oxide support layer (such as a thermally stable metal oxide support layer) can correspond to at least one oxide selected from the corundum group, stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, and mixtures thereof. The weight of metal oxide support can range from 1.0 wt % to 40 wt %, or 2.0 wt % to 30 wt %, or 3.0 wt % to 20 wt %, relative to the total weight of the monolith plus catalyst system.

One category of metal oxide support layers can correspond to traditional refractory oxides that are commonly used to form supported catalysts. For example, the metal oxide support can correspond to α-Al₂O₃, LaAlO₃, LaAl₁₁O₁₈, MgO, CaO, ZrO₂, TiO₂, CeO₂, Y₂O₃, La₂O₃, SiO₂, Na₂O, K₂O, and mixtures thereof. This group is defined herein as the “corundum” group of oxides, although many of the oxides in this group do not have the corundum lattice structure. For example, CeO₂ and MgO can both have a halite crystal structure. α-Al₂O₃ consists essentially of a dense arrangement of oxygen ions in hexagonal closest-packing with Al³⁺ ions in two-thirds of the available octahedral sites. LaAlO₃, often abbreviated as LAO, is an optically transparent ceramic oxide with a distorted perovskite structure. LaAl₁₁O₁₈ can be formed through the solid state reaction of LaAlO₃ and α-Al₂O₃. Plate-like crystals of LaAl₁₁O₁₈ are particularly useful as a metal oxide support since catalytic metals can be trapped between plate-like crystal structures. It suppresses sintering of minute catalytic metals in the active material which is washcoated on the monolith of the catalyst bed. Additional examples of oxides from the corundum group can include, but are not limited to: i) 95 wt % α-Al₂O₃ and 5 wt % SiO₂; ii) 93 wt % α-Al₂O₃, 5 wt % SiO₂ and 2 wt % MgO; iii) 94 wt % α-Al₂O₃, 4 wt % SiO₂, 2 wt % MgO and 1 wt % Na₂O; iv) 95 wt % α-Al₂O₃, 4 wt % SiO2 and 1 wt % TiO₂; v) 7 wt % CeO₂ and 93 wt % MgO; vi) 5 wt % CaO and 95 wt % α-Al₂O₃; vii) 5 wt % MgO, 5 wt % CeO₂ and 90 wt % α-Al₂O₃; viii) 20 wt % ZrO₂ and 80 wt % CeO₂, ix) 5 wt % CeO₂, 20 wt % ZrO₂ and 75 wt % α-Al₂O₃, and x) 6 wt % La₂O₃ and 94 wt % α-Al₂O₃, based on the weight of metal oxide support.

Another category of metal oxides for the metal oxide support layer corresponds to stabilized zirconia. In this discussion, stabilized zirconia as a metal oxide support is defined as an oxide including zirconia (ZrO₂, zirconium oxide) and at least one additive oxide corresponding to Y₂O₃, CaO, MgO, HfO₂, CeO₂, SiO₂, Sc₂O₃, La₂O₃, Al₂O₃, and mixtures thereof. Pure ZrO₂ undergoes a phase transformation from monoclinic (stable at room temperature) to tetragonal (at about 1173° C.) and then to cubic (at about 2370° C.) structures. When a metal oxide support is made from pure zirconia, it can lead to fracture at lowered temperature since it transforms from the tetragonal to the monoclinic structure, which results in a volume expansion. To mitigate this problem, pure ZrO₂ can be stabilized to become the cubic polymorph over the broad range of temperatures. This can be accomplished by substitution of some of the Zr⁴⁺ ions (ionic radius of 0.082 nm) in the crystal lattice with slightly larger ions, such as Y³⁺ ions (ionic radius of 0.096 nm) and/or ions from the other additive oxides. The resulting doped zirconia materials are termed stabilized zirconia. In this invention, the weight of additive oxide in stabilized zirconia can range from 5 wt % to 70 wt %, or 6 wt % to 60 wt %, or 7 wt % to 50 wt %, relative to the total weight of the stabilized zirconia composition. A preferred stabilized zirconia is yttria (Y₂O₃) stabilized zirconia, often abbreviated as YSZ. YSZ is a metal oxide support in which the cubic crystal structure of zirconia is made stable at room temperature by an addition of yttria in the amount of 10 wt % to 30 wt % relative to the total weight of the YSZ. Other examples of stabilized zirconia as a metal oxide support include, but are not limited to: i) 10 wt % Sc₂O₃ stabilized zirconia (ScSZ); ii) 6 wt % Sc₂O₃ and 1 wt % Al₂O₃ stabilized zirconia (ScAlSZ); iii) 65 wt % CeO₂ stabilized zirconia (CSZ); and iv) 30 wt % CeO₂ and 20 wt % Al₂O₃ stabilized zirconia (CeAlSZ).

Still another category of metal oxides for the metal oxide support layer corresponds to perovskite. Perovskite as a metal oxide support is based on the cubic perovskite structure of general formula (ABO₃). The “A”-site and “B”-site can be doped with a host of metal cations, within size constraints. This can allow the properties of the metal oxide support to be tuned to achieve various purposes. The Δ-site cations are larger than the B-site cations. The ideal cubic structure has the B-site cations in 6-fold coordination, surrounded by an octahedron of anions, and the Δ-site cations in 12-fold cuboctahedral coordination. The relative ion size requirements for stability of the cubic structure are quite stringent, so slight buckling and distortion can produce several lower-symmetry distorted versions, in which the coordination numbers of Δ-site cations, B-site cations, or both are reduced. Hence, the doped perovskite structure can be expressed as a chemical formula: A_(x)A′_(1-x)B_(y)B′_(1-y)O_(3-n), wherein A or A′ is an element selected from La, Sr, Ba, Ca, Zr, and Y; wherein B or B′ is an element selected from Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Ga, Zr, Y, and Zn; wherein both x and y are numbers independently selected in the range of 0.0 to 1.0; and wherein n is a number in the range of 0.0 to 0.5. Examples of perovskite structures for the metal oxide support layer can include, but are not limited to, SrTiO₃, CaTiO₃, YAlO₃, LaMnO₃, LaCo_(0.4)Ni_(0.6)O₃ (LCN), Sr_(0.65)La_(0.35)TiO₃ (SLT), BaZr_(0.8)Y_(0.2)O₃ (BZY), La_(0.8)Sr_(0.2)MnO₃ (LSM), La_(0.6)Sr_(0.4)Co_(0.2)Fe_(0.8)O₃ (LSCF), Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O₃ (BSCF), La_(0.6)Sr_(0.4)Co_(0.8)Cr_(0.2)O₃ (LSCC), La_(0.6)Sr_(0.4)Co_(0.8)Mn_(0.2)O₃ (LSCM), La_(0.8)Sr_(0.2)FeO₃ (LSF), and Y_(0.1)Ba_(0.9)CoO₃ (YBC).

Yet another category of metal oxides for the metal oxide support layer corresponds to pyrochlore. Pyrochlore as a metal oxide support is based on the mineral pyrochlore crystal structure of general formula A₂B₂O₇, where the “A” and “B” species are generally rare-earth or transition metal species. The pyrochlore structure is a super structure derivative of the simple fluorite structure. Hence, similar to perovskite, the doped pyrochlore structure can be expressed as a chemical formula: A_(x)A′_(2-x)B_(y)B′_(2-y)O_(7-n), wherein A or A′ is an element selected from La, Sr, Ba, Ca, Gd, Bi, Dy, Tl, Cd, and Y; B or B′ is an element selected from Zr, Ti, Cr, Mn, Fe, Co, Ni, Ru, Mo, and Re; wherein both x and y are numbers independently selected in the range of 0.0 to 2.0; and n is a number in the range of 0.0 to 0.5. Examples of pyrochlore structures for the metal oxide support layer include, but are not limited to, La₂Zr₂O₇, Gd_(1.9)Ca_(0.1)Ti₂O_(6.9), Bi₂Ru₂O₇, Dy₂Ti₂O7, Y₂Mo₂O7, Tl₂Ru₂O₇, and Cd₂Re₂O₇.

Still another category of metal oxides for the metal oxide support layer corresponds to spinel. Spinel as a metal oxide support is based on the spinel structure of general formula AB₂O₄ with the O anions being arranged in a cubic close-packed lattice and the cations “A” and “B” occupying some or all of the octahedral and tetrahedral sites in the lattice. Although the charges of A and B in the prototypical spinel structure are +2 and +3, respectively A²⁺B³⁺ ₂O²⁻ ₄, other combinations incorporating divalent, trivalent, or tetravalent cations, including Mg, Zn, Fe, Mn, Al, Cr, Ti, and Si, are also possible. A and B can also be the same metal with different valences, as is the case with magnetite, Fe₃O₄ (as Fe²⁺Fe³⁺ ₂O²⁻ ₄), which is the most abundant member of the spinel group. Hence, the spinel structure can be expressed as a chemical formula: AB₂O₄, wherein A is an element selected from Mg, Be, Zn, Fe, Ni, Co, Mn, Cu, Ti, Si, and mixtures thereof; and B is an element selected from a group comprising Al, Mg, Fe, Mn, Cr, Co, V, and mixtures thereof. Examples of spinel structures for the metal oxide support include, but are not limited to, MgAl₂O₄, BeAl₂O₄, ZnAl₂O₄, FeAl₂O₄, NiAl₂O₄, MnAl₂O₄, (Mg,Fe)Al₂O₄, CuFe₂O₄, (Fe,Mn,Zn)(Fe,Mn)₂O₄, MnFe₂O₄, MgFe₂O₄, NiFe₂O₄, TiFe₂O₄, (Zn,Fe)Fe₂O₄, FeCr₂O₄, NiCr₂O₄, MgCr₂O₄, ZnCr₂O₄, Mn_(1.5)Co_(1.5)O₄, FeV₂O₄, MgV₂O₄, (Mg,Fe)₂SiO₄, and BeMgAl₄O₈.

Yet another category of metal oxides for the metal oxide support layer corresponds to hibonite. Hibonite as a metal oxide support is based on the mineral hibonite crystal structure of general formula AB₁₂O₁₉, wherein “A” is an element selected from Mg, Ca, Sr, Ba, Fe, Ni, Co, La, Ce, and Y mixtures thereof; and “B” is an element selected from Al, Si, Ti, Zr, Hf, Mg, Ca, and mixtures thereof. Examples of hibonite structures for the metal oxide support include, but are not limited to, CaAl₁₂O₁₉, (Ca,Ce)(Al,Ti,Mg)₁₂O₁₉, (Ca,Ce,La)(Al,Ti,Mg)₁₂O₁₉ and (Fe,Mg)Al₁₂O₁₉. Plate-like crystals of hibonite (Ca,Ce)(Al,Ti,Mg)₁₂O₁₉ can be useful as a metal oxide support since catalytic metals can be trapped between plate-like crystal structures. This can suppress sintering of minute catalytic metals in the active material which is washcoated on the monolith of the catalyst bed.

Still another category of metal oxides for the metal oxide support layer corresponds to zeolite. In this discussion, zeolite as a metal oxide support refers to alumino-silicate materials composed of Si, Al, O, H, optionally further including metals such as Na, Ca, K, Mg, Ti, Sn, Zn, and mixtures thereof, which are members of the family of micro-porous solids known as molecular sieves. The term molecular sieve refers to a particular property of these materials that selectively sort molecules based primarily on a size exclusion process. This is due to a very regular pore structure of molecular dimensions. The maximum size of the molecular or ionic species that can enter the pores of a zeolite is controlled by the dimensions of the channels. These are conventionally defined by the ring size of the aperture, where, for example, the term “8-ring” refers to a closed loop that is built from eight tetrahedrally coordinated silicon (or aluminum) atoms and 8 oxygen atoms. These rings are not always perfectly symmetrical due to a variety of causes, including strain induced by the bonding between units that are needed to produce the overall structure, or coordination of some of the oxygen atoms of the rings to cations within the structure. Zeolite as a metal oxide support in this invention includes over 245 unique zeolite frameworks being produced industrially on a large scale and over 40 naturally occurring zeolite frameworks, Some examples of zeolite that can be used as a metal oxide support include USY Zeolite, L Zeolite, Mordenite Ferrierite, Beta Zeolite, ZSM-5, MCM-68, and mixtures thereof. It is particularly useful for a metal oxide support of the active materials for the low temperature catalytic zone of the RFR since certain zeolite frameworks are known to be structurally stable up to about 750° C. The stable micro-pores of zeolite provide extensive surface area for catalytic metal dispersion. Other examples of zeolite as a metal oxide support include various types of Faujasite. This can include Faujasite-Na, Faujasite-Mg and Faujasite-Ca. The Faujasites all share the same basic formula, (Na₂,Ca,Mg)_(3.5)[Al₇Si₁₇O₄₈]₃₂(H₂O), by varying the amounts of sodium, magnesium and calcium. Faujasite is synthesized, as are other zeolites, from alumina sources such as sodium aluminate and silica sources such as sodium silicate. Other alumino-silicates such as kaolin are used as well. The ingredients are dissolved in a basic environment such as sodium hydroxide aqueous solution and crystallized at 70 to 300° C. After crystallization the Faujasite is in its sodium form and can be ion exchanged with ammonium to improve stability. The ammonium ion is removed later by calcination which renders the zeolite in its acid form. Depending on the silica-to-alumina ratio of their framework, synthetic Faujasite zeolites are divided into X and Y zeolites. In X zeolites the silica-to-alumina ratio is between 2 and 3, while in Y zeolites the ratio is 3 or higher. The negative charges of the framework are balanced by the positive charges of cations in non-framework positions. Such zeolites have ion-exchange, catalytic and adsorptive properties. The stability of the zeolite increases with the silica-to-alumina ratio of the framework. It is also affected by the type and amount of cations located in non-framework positions. For catalytic cracking, the Y zeolite is often used in a rare earth-hydrogen exchanged form. By using thermal, hydrothermal or chemical methods, some of the alumina can be removed from the Y zeolite framework, resulting in high-silica Y zeolites. Such zeolites are used in cracking and hydrocracking catalysts. Complete delamination results in Faujasite-silica. Still another examples of a zeolite that can be used as a metal oxide support layer is Chabazite, with formula (Ca, Na₂, K₂, Mg)Al₂Si₄O₁₂.6H₂O. Recognized varieties include Chabazite-Ca, Chabazite-K, Chabazite-Na, and Chabazite-Sr, depending on the prominence of the indicated cation. Chabazite crystallizes in the triclinic crystal system with typically rhombohedral shaped crystals.

Structure (Monolith) for Supporting Catalyst System

One of the purposes of using a monolith or another supporting structure within a reforming environment is to increase the available surface area for holding a deposited catalyst/catalyst system. To achieve this, some monoliths correspond to a structure with a large plurality of cells or passages that allow gas flow through the monolith. Because each individual cell provides surface area for deposition of catalyst, including a large number of cells or passages per unit area can substantially increase the available surface area for catalyst.

Generally, the monolith or other structure used to support the catalyst/catalyst system can be formed from a material is denoted by the formula (PQ). P can be at least one metal selected from the group consisting of Al, Si, Mg, Ca, Sr, Ba, K, Na, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ni, Co, Y, La, Ce, and mixtures thereof. Q is oxide. Thus, the monolith material (PQ) is a metal oxide.

In some preferred aspects, the metal oxide can correspond to aluminum oxide (a.k.a. alumina), Al₂O₃. The preferred Al₂O₃ in this invention is α-Al₂O₃. While α-Al₂O₃ is the preferred crystalline phase, another phase containing sodium oxide (Na₂O), which is sometimes an unavoidable impurity in α-Al₂O₃, could be also present, namely Na₂O(Al₂O₃)₁₁ or NaAl₅O₈.

Optionally, the monolith or structure material (PQ) can be α-Al₂O₃ containing at least one additive oxide selected from the group consisting of Sift, MgO, CaO, TiO₂, Na₂O, K₂O, and mixtures thereof. The weight of additive oxide in the monolith materials composition can range from 0.1 wt % to 15 wt %, or 1.0 wt % to 10 wt %, or 2.0 wt % to 8.0 wt %, relative to the total weight of the monolith materials composition. As non-limiting illustrative examples, the monolith material (PQ) can be: i) 95 wt % α-Al₂O₃ and 5 wt % SiO₂, ii) 93 wt % α-Al₂O₃, 5 wt % SiO₂ and 2 wt % MgO, iii) 93 wt % α-Al₂O₃, 4 wt % SiO₂, 2 wt % MgO and 1 wt % Na₂O, and iv) 95 wt % α-Al₂O₃, 4 wt % SiO₂ and 1 wt. % TiO₂.

In other aspects, the monolith material (PQ) can be partially composed or substantially composed of non-alumina based oxides. As non-limiting illustrative examples, the monolith material (PQ) can be silica (Sift), magnesia (MgO), ceria (CeO₂), titania (TiO₂), zirconia (ZrO₂), cordierite (2MgO 2Al₂O₃ 2SiO₂), mullite (3Al₂O₃ 2SiO₂), aluminum titanate (Al₂TiO₅), magnesium aluminate (MgAl₂O₄), calcium-stabilized zirconia (CaO—ZrO₂), magnesium-stabilized zirconia (MgO—ZrO₂), yttria-stabilized zirconia (Y₂O₃—ZrO₂), yttria (Y₂O₃), barium zirconate (BaZrO₃), strontium zirconate (SrZrO₃), and mixtures thereof. Still other examples of potential monolith materials include SiC, Si₃N₄, yttrium-stabilized zirconia, and Al₂TiO₅ ceramics. It is noted that SiC and Si₃N₄ do not follow the (PQ) structural formula.

In some aspects, the monolith material (PQ) can further include supplementary components. Such supplementary components can facilitate easy extrusion and correspond to additional structural components within the monolith material composition. For example, the monolith material composition may further comprise one or more silicates comprising a metal selected from the group consisting of Al, Si, Ca, Mg, K, Na, Y, Zr, Hf, Ti, Cr, Mn, Fe, Ni, Co, and mixtures thereof. One example is bentonite, which is an aluminum phyllosilicate clay composed mostly of montmorillonite. The different types of bentonite are each named after the respective dominant element, such as potassium (K), sodium (Na), calcium (Ca), and aluminum (Al). For example, the chemical formula of sodium bentonite is Al₂H₂Na₂O₁₃Si₄. Some hydroxyl ions (OH—) can be present in silicates, but under high temperature calcination and sintering conditions, such hydroxyl groups can be converted to oxide form. Yet another example is talc, a clay mineral composed of hydrated magnesium silicate with the chemical formula Mg₃Si₄O₁₀(OH)₂. Due to its nature of basal cleavage and uneven flat fracture, it is foliated with a two-dimensional plate form which is beneficial in extrusion of the monolith material.

In various aspects, a monolith or other structure for providing a surface for the reforming catalyst system may be prepared by manufacturing techniques such as but not limited to conventional ceramic powder manufacturing and processing techniques, e.g., mixing, milling, degassing, kneading, pressing, extruding, casting, drying, calcining, and sintering. The starting materials can correspond to a suitable ceramic powder and an organic binder powder in a suitable volume ratio. Certain process steps may be controlled or adjusted to obtain the desired grain size and porosity range and performance properties, such as by inclusion of various manufacturing, property adjusting, and processing additives and agents as are generally known in the art. For example, the two or more types of oxide powders may be mixed in the presence of an organic binder and one or more appropriate solvents for a time sufficient to substantially disperse the powders in each other. As another example, precursors of the oxides present in a monolith may be dissolved in water at a desired ratio, spray dried, and calcined to make a mixed powder. Such precursors include (but are not limited to) chlorides, sulfates, nitrates, and mixtures thereof. The calcined powder can be further mixed in the presence of an organic binder and appropriate solvent(s) to make a mixed “dough”. Then, the mixed “dough” of materials can be placed in a die or form, extruded, dried or otherwise formed into a desired shape. The resulting “green body” can then be sintered at temperatures in the range of about 1200° C.˜1700° C. for at least ten minutes, such as from 10 minutes to 10 hours, or possibly from 10 minutes up to 48 hours or still longer.

The sintering operation may be performed in an oxidizing atmosphere, reducing atmosphere, or inert atmosphere, and at ambient pressure or under vacuum. For example, the oxidizing atmosphere could be air or oxygen, the inert atmosphere could be argon, and a reducing atmosphere could be hydrogen, CO/CO₂ or H₂/H₂O mixtures. Thereafter, the sintered body is allowed to cool, typically to ambient conditions. The cooling rate may also be controlled to provide a desired set of grain and pore structures and performance properties in the particular component.

In some aspects, the monolith material (PQ) can further include an intermediate bond layer. The intermediate bond layer can be applied on monolith surfaces prior to washcoat active materials comprising metal oxide support and catalytic metal. The intermediate bond layer provides a better adherence to the washcoated active material. The intermediate bond layer is a metal oxide, (M)_(x)O_(y), wherein (M) is at least one metal selected from the group consisting of Al, Si, Mg, Ca, Sr, Ba, K, Na, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ni, Co, Y, La, Ce, and mixtures thereof. Aluminum oxide (a.k.a. alumina), Al₂O₃, is a preferred metal oxide for the bond layer. As an example of how to form an intermediate bond layer, the selected metal oxide, (M)_(x)O_(y), can be dispersed in a solution to form a slurry. The slurry can then be washcoated on the monolith. The monolith washcoated with the selected metal oxide, (M)_(x)O_(y), is dried and sintered at temperatures in the range of 1100° C.˜1600° C. to make the intermediate bonding layer.

It has been discovered that limiting the maximum porosity in the final sintered body tends to effectively, if not actually, limit interconnectivity of the pore spaces with other pore spaces to an extent that increases or maximizes volumetric heat capacity of the sintered body. The porosity ranges for a monolith or other structure can depend upon the desired final component performance properties, but are within a range defined by one or more of the minimum porosity values and one or more of the maximum porosity values, or any set of values not expressly enumerated between the minimums and maximums. Examples of suitable porosity values are 0 vol % to 20 vol % porosity, or 0 vol % to 15 vol %, or 0 vol % to 10 vol %, or 0 vol % to 5 vol %.

The sintered monolith and/or other formed ceramic structure can have any convenient shape suitable for use as a surface for receiving a catalyst or catalyst system. An example of a monolith can be an extruded honeycomb monolith. Honeycomb monoliths can be extruded structures that comprise many (e.g., a plurality, meaning more than one) small gas flow passages or conduits, arranged in parallel fashion with thin walls in between. A small reactor may include a single monolith, while a larger reactor can include a number of monoliths, while a still larger reactor may be substantially filled with an arrangement of many honeycomb monoliths. Each monolith may be formed by extruding monolith blocks with shaped (e.g., square, trigonal, or hexagonal) cross-section and two- or three-dimensionally stacking such blocks above, behind, and beside each other. Monoliths can be attractive as reactor internal structures because they provide high heat transfer capacity with minimum pressure drop.

In some aspects, honeycomb monoliths can be characterized as having open frontal area (or geometric void volume) between 25% and 55%, and having conduit density between 50 and 2000 pores or cells per square inch (CPSI), or between 100 and 900 cells per square inch, or between 100 cells per square inch to 600 cells per square inch. For example, in one embodiment, the conduits may have a diameter/characteristic cell side length of only a few millimeters, such as on the order of roughly one millimeter. Reactor media components, such as the monoliths or alternative bed media, can provide for channels that include a packing with an average wetted surface area per unit volume that ranges from 50 ft⁻¹ to 3000 ft⁻¹ (˜0.16 km⁻¹ to ˜10 km⁻¹), or from 100 ft⁻¹ to 2500 ft⁻¹ (˜0.32 km⁻¹ to ˜8.2 km⁻¹), or from 200 ft⁻¹ to 2000 ft⁻¹ (˜0.65 km⁻¹ to ˜6.5 km⁻¹), based upon the volume of the first reactor that is used to convey a reactant. These relatively high surface area per unit volume values can aid in achieving a relatively quick change in the temperature through the reactor, such as generally illustrated by the relatively steep slopes in the exemplary temperature gradient profile graphs shown in FIG. 1(a) or 1(b) of FIG. 1.

Reactor media components can also provide for channels that include a packing that includes a high volumetric heat transfer coefficient (e.g., 0.02 cal/cm³ s° C. or more, or 0.05 cal/cm³ s° C. or more, or 0.10 cal/cal/cm³ s° C. or more); that have low resistance to flow (low pressure drop); that have an operating temperature range consistent with the highest temperatures encountered during regeneration; that have high resistance to thermal shock; and/or that have high bulk heat capacity (e.g., 0.10 cal/cm³ s° C. or more, or 0.20 cal/cm³ s° C. or more). As with the high surface area values, these relatively high volumetric heat transfer coefficient values and/or other properties can aid in achieving a relatively quick change in the temperature through the reactor, such as generally illustrated by the relatively steep slopes in the exemplary temperature gradient profile graphs, such as in FIGS. 1(a) and 1(b) of FIG. 1. The cited values are averages based upon the volume of reactor used for conveyance of a reactant.

In various aspects, adequate heat transfer rate can be characterized by a heat transfer parameter, ΔTHT, below 500° C., or below 100° C., or below 50° C. The parameter ΔTHT, as used herein, is the ratio of the bed-average volumetric heat transfer rate that is needed for recuperation, to the volumetric heat transfer coefficient of the bed, hv. The volumetric heat transfer rate (e.g. cal/cm³ sec) that is sufficient for recuperation can be calculated as the product of the gas flow rate (e.g. g/sec) with the gas heat capacity (e.g. cal/g° C.) and desired end-to-end temperature change (excluding any reaction, e.g. ° C.), and then this quantity can be divided by the volume (e.g. cm³) of the reactor (or portion of a reactor) traversed by the gas. The volumetric heat transfer coefficient of the bed, hv, can typically be calculated as the product of an area-based coefficient (e.g. cal/cm² s° C.) and a specific surface area for heat transfer (av, e.g. cm²/cm³), often referred to as the wetted area of the packing.

Multiple Zone Catalyst System

In some aspects, reforming can be further improved by using multiple catalysts in the catalyst system. In such aspects, different regions of the reaction zone can include different catalysts. Due to the nature of a reverse flow reactor, a temperature profile can develop within the reactor so that some reaction zones are at higher temperatures while other zones are at lower temperatures. By using a catalyst system including a plurality of catalysts, the catalyst in a reaction zone can be selected to provide improved activity for the temperature in that reaction zone based on the temperature profile.

FIG. 4 shows an example of temperature profiles obtained during steam reforming of a methane feed in a 12 inch (˜30 cm) pilot scale reverse flow reactor. The pilot scale reactor included multiple catalyst zones, with a first (higher temperature) zone including a nickel-based catalyst and a second (lower temperature) zone including a rhodium-based catalyst. For the pilot reactor used to generate the temperature profile in FIG. 4, the reforming zone of the reactor corresponds to inches 4-12 of the reactor. The portion of the reactor from 0-4 inches corresponds to the inlet end of the reactor for the regeneration gas flows. The location at roughly 4 inches into the reactor corresponds to the location where combustion of the regeneration gas flows occurs. As shown in FIG. 4, the temperature profile at the end of the regeneration step is higher in temperature than the temperature profile at the end of the reforming step. This is due to the cycles of consuming heat during reforming and then replenishing heat during regeneration. However, the overall shape of the temperature profile is similar after both the reforming step and the regeneration step. It is believed that the general shape of the temperature profile is also present at intermediate times.

Based on the example of a temperature profile shown in FIG. 4, during operation of a reverse flow reactor for reforming, certain zones in the reactor are at higher temperatures while other zones in the reactor are at intermediate or lower temperatures. Because the location of the high, intermediate, and low temperature zones is relatively stable during a reaction cycle, it has been discovered that further benefits can be obtained by using catalysts that have improved activity for the types of temperatures in a given zone of the reactor.

When multiple catalyst zones are used in a reactor, any convenient number of zones can be used. Thus, when a plurality of catalyst zones are present, the number of catalyst zones can range from 2 zones to 10 zones, or 2 zones to 6 zones, or 3 zones to 10 zones, or 3 zones to 6 zones. Of course, since it is also possible to have a single catalyst zone, in some aspects the number of catalyst zones can range from 1 zone to 10 zones, or 1 zone to 6 zones.

The temperature profile in FIG. 4 can be used to illustrate the concept of using multiple catalyst zones. One way to organize catalyst zones with a temperature profile similar to FIG. 3 can be to use two zones corresponding to a high temperature catalyst zone and a low temperature catalyst zone. For example, for the reactor used to generate the temperature profile in FIG. 4, inches 4-6 (or inches 4-7) of the reactor could correspond to a high temperature zone, while inches 6-12 (or inches 7-12) of the reactor could correspond to a low temperature zone. Another option could be to use three zones, with a high temperature, intermediate temperature, and low temperature zone. For example, for the reactor used to generate the temperature profile in FIG. 4, inches 4-6 could correspond to a high temperature zone, inches 6-9 could correspond to an intermediate temperature zone, and inches 9-12 could correspond to a low temperature zone. Still other options for organizing a reactor into two zones, three zones, four zones, or any other convenient number of zones are also available, depending on the desired catalyst system and the temperature profile of a reactor.

In some aspects, when different catalyst systems are used in different zones, the zones can be characterized based on the peak temperature within the different zones. For example, the peak temperature in a first zone can be greater than the peak temperature in a second zone by 100° C. or more, or 200° C. or more, or 300° C. or more, such as up to 700° C. or possibly still higher. The peak temperature within a zone refers to the location within the zone that has the highest average temperature at the end of the regeneration step. The average temperature at a location at the end of the regeneration cycle can be calculated based on averaging the temperature at the end of the regeneration step over 10 full cycles.

Modification of Regeneration Step

It is noted that NiO/NiAl₂O₄ is an example of a catalyst system where the catalytic metal can be converted from an oxide state to a reduced metallic state under the high temperature reforming conditions. To the degree that such reduction of the catalytic metal occurs, it has been discovered that it is desirable to return the catalytic metal to a fully oxidized state prior to the next reforming step.

In various aspects, returning a reduced metal to a fully oxidized state prior to the next reforming step can be accomplished by increasing the amount of excess oxygen that is used during the regeneration (combustion) step that is used to add heat to the reactor. Conventionally, the amount of oxygen used during a regeneration step is slightly greater than the stoichiometric amount needed for full combustion of the fuel used during regeneration. In this discussion, 100% of the molar stoichiometric oxygen amount is defined as the stoichiometric amount of oxygen that is needed to combust all fuel introduced during the regeneration step. Amounts of oxygen greater than 100% of the molar stoichiometric oxygen amount correspond to excess oxygen. For example, 120% of the molar stoichiometric oxygen amount corresponds using a number of moles of oxygen that is 20% greater than the number of moles needed for stoichiometric combustion. This can be referred to an excess molar oxygen amount of 20%. Because of the large flow volumes and high superficial gas velocities already present, addition of still further gas to either the regeneration step or the reforming step is generally not desirable. However, it has been discovered that increasing the amount of excess oxygen used during regeneration can improved reforming activity by allowing any reduced catalytic metal formed during the reforming step to be oxidized during the regeneration step. In various aspects, the amount of oxygen used during regeneration can correspond to 120% or more of the molar stoichiometric amounts, or 125% or more, or 130% or more, or 140% or more, such as up to 200% or possibly still higher. This corresponds to an excess molar oxygen amount of 20% or more, or 25% or more, or 30% or more, or 40% or more, such as up to 100% or possibly still higher.

Process Example—Reverse Flow Reforming and Regeneration

In various aspects, reforming of hydrocarbons can be performed under steam reforming conditions in the presence of H₂O, under dry reforming conditions in the presence of CO₂, or under conditions where both H₂O and CO₂ are present in the reaction environment. As a general overview of operation during reforming in a swing reactor, such as a reverse flow reactor, a regeneration step or portion of a reaction cycle can be used to provide heat for the reactor. Reforming can then occur within the reactor during a reforming step or portion of the cycle, with the reforming reaction consuming heat provided during the reactor regeneration step. During reactor regeneration, fuel and an oxidant are introduced into the reactor from a regeneration end of the reactor. The bed and/or monoliths in the regeneration portion of the reactor can absorb heat, but typically do not include a catalyst for reforming. As the fuel and oxidant pass through the regeneration section, heat is transferred from the regeneration section to the fuel and oxidant. Combustion does not occur immediately, but instead the location of combustion is controlled to occur in a middle portion of the reactor. The flow of the reactants continues during the regeneration step, leading to additional transfer of the heat generated from combustion into the reforming end of the reactor.

After a sufficient period of time, the combustion reaction is stopped. Any remaining combustion products and/or reactants can optionally be purged. The reforming step or portion of the reaction cycle can then start. The reactants for reforming can be introduced into the reforming end of the reactor, and thus flow in effectively the opposite direction relative to the flow during regeneration. The bed and/or monoliths in the reforming portion of the reactor can include a catalyst for reforming. In various aspects, at least a portion of the catalyst can correspond to a catalyst formed from a ceramic composition as described herein. As reforming occurs, the heat introduced into the reforming zone during combustion can be consumed by the endothermic reforming reaction. After exiting the reforming zone, the reforming products (and unreacted reactants) are no longer exposed to a reforming catalyst. As the reforming products pass through the regeneration zone, heat can be transferred from the products to the regeneration zone. After a sufficient period of time, the reforming process can be stopped, remaining reforming products can optionally be collected or purged from the reactor, and the cycle can start again with a regeneration step.

The reforming reaction performed within the reactor can correspond reforming of methane and/or other hydrocarbons using steam reforming, in the presence of H₂O; using dry reforming, in the presence of CO₂, or using “bi” reforming in the presence of both H₂O and CO₂. Examples of stoichiometry for steam, dry, and “bi” reforming of methane are shown in equations (1)-(3).

Dry Reforming: CH₄+CO₂=2CO+2H₂  (1)

Steam Reforming: CH₄+H₂O=CO+3H₂  (2)

Bi Reforming: 3CH₄+2H₂O+CO₂=4CO+8H₂.  (3)

As shown in equations (1)-(3), dry reforming can produce lower ratios of H₂ to CO than steam reforming. Reforming reactions performed with only steam can generally produce a ratio of H₂ to CO of around 3, such as 2.5 to 3.5. By contrast, reforming reactions performed in the presence of CO₂ can generate much lower ratios, possibly approaching a ratio of H₂ to CO of roughly 1.0 or even lower. By using a combination of CO₂ and H₂O during reforming, the reforming reaction can potentially be controlled to generate a wide variety of H₂ to CO ratios in a resulting syngas.

It is noted that the ratio of H₂ to CO in a synthesis gas can also be dependent on the water gas shift equilibrium. Although the above stoichiometry shows ratios of roughly 1 or roughly 3 for dry reforming and steam reforming, respectively, the equilibrium amounts of H₂ and CO in a synthesis gas can be different from the reaction stoichiometry. The equilibrium amounts can be determined based on the water gas shift equilibrium, which relates the concentrations of H₂, CO, CO₂ and H₂O based on the reaction:

H₂O+CO⇔H₂+CO₂.  (4)

Most reforming catalysts, such as rhodium and/or nickel, can also serve as water gas shift catalysts. Thus, if reaction environment for producing H₂ and CO also includes H₂O and/or CO₂, the initial stoichiometry from the reforming reaction may be altered based on the water gas shift equilibrium. This equilibrium is also temperature dependent, with higher temperatures favoring production of CO and H₂O. It is noted that higher temperatures can also improve the rate for reaching equilibrium. As a result, the ability to perform a reforming reaction at elevated temperatures can potentially provide several benefits. For example, instead of performing steam reforming in an environment with excess H₂O, CO₂ can be added to the reaction environment. This can allow for both a reduction in the ratio of H₂ to CO produced based on the dry reforming stoichiometry as well as a reduction in the ratio of H₂ to CO produced based on the water gas shift equilibrium. Alternatively, if a higher H₂ to CO ratio is desired, CO₂ can be removed from the environment, and the ratio of H₂O to CH₄ (or other hydrocarbons) can be controlled to produce a desirable type of synthesis gas. This can potentially allow for generation of a synthesis gas having a H₂ to CO ratio of 0.1 to 15, or 0.1 to 3.0, or 0.5 to 5.0, or 1.0 to 10, by selecting appropriate amounts of feed components.

The reforming reactions shown in equations (1)-(3) are endothermic reactions. One of the challenges in commercial scale reforming can be providing the heat for performing the reforming reaction in an efficient manner while reducing or minimizing introduction of additional components into the desired synthesis gas product. Cyclic reaction systems, such as reverse flow reactor systems, can provide heat in a desirable manner by having a cycle including a reforming step and a regeneration step. During the regeneration step, combustion can be performed within a selected area of the reactor. A gas flow during regeneration can assist with transferring this heat from the combustion zone toward additional portions of the reforming zone in the reactor. The reforming step within the cycle can be a separate step, so that incorporation of products from combustion into the reactants and/or products from reforming can be reduced or minimized. The reforming step can consume heat, which can reduce the temperature of the reforming zone. As the products from reforming pass through the reactor, the reforming products can pass through a second zone that lacks a reforming or water gas shift catalyst. This can allow the reaction products to cool prior to exiting the reactor. The heat transferred from the reforming products to the reactor can then be used to increase the temperature of the reactants for the next combustion or regeneration step.

One common source for methane is natural gas. In some applications, natural gas, including associated hydrocarbon and impurity gases, may be used as a feed for the reforming reaction. The supplied natural gas also may be sweetened and/or dehydrated natural gas. Natural gas commonly includes various concentrations of associated gases, such as ethane and other alkanes, preferably in lesser concentrations than methane. The supplied natural gas may include impurities, such as H₂S and nitrogen. More generally, the hydrocarbon feed for reforming can include any convenient combination of methane and/or other hydrocarbons. Optionally, the reforming feed may also include some hydrocarbonaceous compounds, such as alcohols or mercaptans, which are similar to hydrocarbons but include one or more heteroatoms different from carbon and hydrogen. In some aspects, an additional component present in the feed can correspond to impurities such as sulfur that can adsorb to the catalytic monolith during a reducing cycle (such as a reforming cycle). Such impurities can be oxidized in a subsequent cycle to form sulfur oxides, which can then be reduced to release additional sulfur-containing components (or other impurity-containing components) into the reaction environment.

In some aspects, the feed for reforming can include, relative to a total weight of hydrocarbons in the feed for reforming, 5 wt % or more of C₂₊ compounds, such as ethane or propane, or 10 wt % or more, or 15 wt % or more, or 20 wt % or more, such as up to 50 wt % or possibly still higher. It is noted that nitrogen and/or other gases that are non-reactive in a combustion environment, such as H₂O and CO₂, may also be present in the feed for reforming. In aspects where the reformer corresponds to an on-board reforming environment, such non-reactive products can optionally be introduced into the feed, for example, based on recycle of an exhaust gas into the reformer. Additionally or alternately, the feed for reforming can include 40 wt % or more methane, or 60 wt % or more, or 80 wt % or more, or 95 wt % or more, such as having a feed that is substantially composed of methane (98 wt % or more). In aspects where the reforming corresponds to steam reforming, a molar ratio of steam molecules to carbon atoms in the feed can be 0.3 to 4.0. It is noted that methane has 1 carbon atom per molecule while ethane has 2 carbon atoms per molecule. In aspects where the reforming corresponds to dry reforming, a molar ratio of CO₂ molecules to carbon atoms in the feed can be 0.05 to 3.0.

Within the reforming zone of a reverse flow reactor, the temperature can vary across the zone due to the nature of how heat is added to the reactor and/or due to the kinetics of the reforming reaction. The highest temperature portion of the zone can typically be found near a middle portion of the reactor. This middle portion can be referred to as a mixing zone where combustion is initiated during regeneration. At least a portion of the mixing zone can correspond to part of the reforming zone if a monolith with reforming catalyst extends into the mixing zone. As a result, the location where combustion is started during regeneration can typically be near to the end of the reforming zone within the reactor. Moving from the center of the reactor to the ends of the reactor, the temperature can decrease. As a result, the temperature at the beginning of the reforming zone (at the end of the reactor) can be cooler than the temperature at the end of the reforming zone (in the middle portion of the reactor).

As the reforming reaction occurs, the temperature within the reforming zone can be reduced. The rate of reduction in temperature can be related to the kinetic factors of the amount of available hydrocarbons for reforming and/or the temperature at a given location within the reforming zone. As the reforming feed moves through the reforming zone, the reactants in the feed can be consumed, which can reduce the amount of reforming that occurs at downstream locations. However, the increase in the temperature of the reforming zone as the reactants move across the reforming zone can lead to an increased reaction rate.

At roughly 500° C., the reaction rate for reforming can be sufficiently reduced that little or no additional reforming will occur. As a result, in some aspects as the reforming reaction progresses, the beginning portion of the reforming zone can cool sufficiently to effectively stop the reforming reaction within a portion of the reforming zone. This can move the location within the reactor where reforming begins to a location that is further downstream relative to the beginning of the reforming zone. When a sufficient portion of the reforming zone has a temperature below 500° C., or below 600° C., the reforming step within the reaction cycle can be stopped to allow for regeneration. Alternatively, based on the amount of heat introduced into the reactor during regeneration, the reforming portion of the reaction cycle can be stopped based on an amount of reaction time, so that the amount of heat consumed during reforming (plus heat lost to the environment) is roughly in balance with the amount of heat added during regeneration. After the reforming process is stopped, any remaining synthesis gas product still in the reactor can optionally be recovered prior to starting the regeneration step of the reaction cycle.

The regeneration process can then be initiated. During regeneration, a fuel such as methane, natural gas, or H₂, and oxygen can be introduced into the reactor and combusted. The location where the fuel and oxidant are allowed to mix can be controlled in any convenient manner, such as by introducing the fuel and oxidant via separate channels. By delaying combustion during regeneration until the reactants reach a central portion of the reactor, the non-reforming end of the reactor can be maintained at a cooler temperature. This can also result in a temperature peak in a middle portion of the reactor. The temperature peak can be located within a portion of the reactor that also includes the reforming catalyst. During a regeneration cycle, the temperature within the reforming reactor can be increased sufficiently to allow for the reforming during the reforming portion of the cycle. This can result in a peak temperature within the reactor of 1100° C. or more, or 1200° C. or more, or 1300° C. or more, or potentially a still higher temperature.

The relative length of time and reactant flow rates for the reforming and regeneration portions of the process cycle can be selected to balance the heat provided during regeneration with the heat consumed during reforming. For example, one option can be to select a reforming step that has a similar length to the regeneration step. Based on the flow rate of hydrocarbons, H₂O, and/or CO₂ during the reforming step, an endothermic heat demand for the reforming reaction can be determined. This heat demand can then be used to calculate a flow rate for combustion reactants during the regeneration step. Of course, in other aspects the balance of heat between reforming and regeneration can be determined in other manners, such as by determining desired flow rates for the reactants and then selecting cycle lengths so that the heat provided by regeneration balances with the heat consumed during reforming.

In addition to providing heat, the reactor regeneration step during a reaction cycle can also allow for coke removal from the catalyst within the reforming zone. In various aspects, one or more types of catalyst regeneration can potentially occur during the regeneration step. One type of catalyst regeneration can correspond to removal of coke from the catalyst. During reforming, a portion of the hydrocarbons introduced into the reforming zone can form coke instead of forming CO or CO₂. This coke can potentially block access to the catalytic sites (such as metal sites) of the catalyst. In some aspects, the rate of formation can be increased in portions of the reforming zone that are exposed to higher temperatures, such as portions of the reforming zone that are exposed to temperatures of 800° C. or more, or 900° C. or more, or 1000° C. or more. During a regeneration step, oxygen can be present as the temperature of the reforming zone is increased. At the temperatures achieved during regeneration, at least a portion of the coke generated during reforming can be removed as CO or CO₂.

Due to the variation in temperature across the reactor, several options can be used for characterizing the temperature within the reactor and/or within the reforming zone of the reactor. One option for characterizing the temperature can be based on an average bed or average monolith temperature within the reforming zone. In practical settings, determining a temperature within a reactor requires the presence of a measurement device, such as a thermocouple. Rather than attempting to measure temperatures within the reforming zone, an average (bed or monolith) temperature within the reforming zone can be defined based on an average of the temperature at the beginning of the reforming zone and a temperature at the end of the reforming zone. Another option can be to characterize the peak temperature within the reforming zone after a regeneration step in the reaction cycle. Generally, the peak temperature can occur at or near the end of the reforming zone, and may be dependent on the location where combustion is initiated in the reactor. Still another option can be to characterize the difference in temperature at a given location within the reaction zone at different times within a reaction cycle. For example, a temperature difference can be determined between the temperature at the end of the regeneration step and the temperature at the end of the reforming step. Such a temperature difference can be characterized at the location of peak temperature within the reactor, at the entrance to the reforming zone, at the exit from the reforming zone, or at any other convenient location.

In various aspects, the reaction conditions for reforming hydrocarbons can include one or more of an average reforming zone temperature ranging from 400° C. to 1200° (or more); a peak temperature within the reforming zone of 800° C. to 1500° C.; a temperature difference at the location of peak temperature between the end of a regeneration step and the end of the subsequent reforming step of 25° C. or more, or 50° C. or more, or 100° C. or more, or 200° C. or more, such as up to 800° C. or possibly still higher; a temperature difference at the entrance to the reforming zone between the end of a regeneration step and the end of the subsequent reforming step of 25° C. or more, or 50° C. or more, or 100° C. or more, or 200° C. or more, such as up to 800° C. or possibly still higher; and/or a temperature difference at the exit from the reforming zone between the end of a regeneration step and the end of the subsequent reforming step of 25° C. or more, or 50° C. or more, or 100° C. or more, or 200° C. or more, such as up to 800° C. or possibly still higher.

With regard to the average reforming zone temperature, in various aspects the average temperature for the reforming zone can be 500° C. to 1500° C., or 400° C. to 1200° C., or 800° C. to 1200° C., or 400° C. to 900° C., or 600° C. to 1100° C., or 500° C. to 1000° C. Additionally or alternately, with regard to the peak temperature for the reforming zone (likely corresponding to a location in the reforming zone close to the location for combustion of regeneration reactants), the peak temperature can be 800° C. to 1500° C., or 1000° C. to 1400° C., or 1200° C. to 1500° C., or 1200° C. to 1400° C.

Additionally or alternately, the reaction conditions for reforming hydrocarbons can include a pressure of 0 psig to 1500 psig (10.3 MPa), or 0 psig to 1000 psig (6.9 MPa), or 0 psig to 550 psig (3.8 MPa); and a gas hourly space velocity of reforming reactants of 1000 hr⁻¹ to 50,000 hr⁻¹. The space velocity corresponds to the volume of reactants relative to the volume of monolith per unit time. The volume of the monolith is defined as the volume of the monolith as if it was a solid cylinder.

In some aspects, an advantage of operating the reforming reaction at elevated temperature can be the ability to convert substantially all of the methane and/or other hydrocarbons in a reforming feed. For example, for a reforming process where water is present in the reforming reaction environment (i.e., steam reforming or bi-reforming), the reaction conditions can be suitable for conversion of 10 wt % to 100 wt % of the methane in the reforming feed, or 20 wt % to 80 wt %, or 50 wt % to 100 wt %, or 80 wt % to 100 wt %, or 10 wt % to 98 wt %, or 50 wt % to 98 wt %. Additionally or alternately, the reaction conditions can be suitable for conversion of 10 wt % to 100 wt % of the hydrocarbons in the reforming feed, or 20 wt % to 80 wt %, or 50 wt % to 100 wt %, or 80 wt % to 100 wt %, or 10 wt % to 98 wt %, or 50 wt % to 98 wt %.

In other aspects, for a reforming process where carbon dioxide is present in the reforming reaction environment (i.e., dry reforming or bi-reforming), the reaction conditions can be suitable for conversion of 10 wt % to 100 wt % of the methane in the reforming feed, or 20 wt % to 80 wt %, or 50 wt % to 100 wt %, or 80 wt % to 100 wt %, or 10 wt % to 98 wt %, or 50 wt % to 98 wt %. Additionally or alternately, the reaction conditions can be suitable for conversion of 10 wt % to 100 wt % of the hydrocarbons in the reforming feed, or 20 wt % to 80 wt %, or 50 wt % to 100 wt %, or 80 wt % to 100 wt %, or 10 wt % to 98 wt %, or 50 wt % to 98 wt %.

In some alternative aspects, the reforming reaction can be performed under dry reforming conditions, where the reforming is performed with CO₂ as a reagent but with a reduced or minimized amount of H₂O in the reaction environment. In such alternative aspects, a goal of the reforming reaction can be to produce a synthesis gas with a H₂ to CO ratio of 1.0 or less. In some aspects, the temperature during reforming can correspond to the temperature ranges described for steam reforming. Optionally, in some aspects a dry reforming reaction can be performed at a lower temperature of between 500° C. to 700° C., or 500° C. to 600° C. In such aspects, the ratio of H₂ to CO can be 0.3 to 1.0, or 0.3 to 0.7, or 0.5 to 1.0. Performing the dry reforming reaction under these conditions can also lead to substantial coke production, which can require removal during regeneration in order to maintain catalytic activity.

Example of Reverse Flow Reactor Configuration

For endothermic reactions operated at elevated temperatures, such as hydrocarbon reforming, a reverse flow reactor can provide a suitable reaction environment for providing the heat for the endothermic reaction.

In a reverse flow reactor, the heat needed for an endothermic reaction may be provided by creating a high-temperature heat bubble in the middle of the reactor. A two-step process can then be used wherein heat is (a) added to the reactor bed(s) or monolith(s) via in-situ combustion, and then (b) removed from the bed in-situ via an endothermic process, such as reforming, pyrolysis, or steam cracking. This type of configuration can provide the ability to consistently manage and confine the high temperature bubble in a reactor region(s) that can tolerate such conditions long term. A reverse flow reactor system can allow the primary endothermic and regeneration processes to be performed in a substantially continuous manner.

A reverse flow reactor system can include first and second reactors, oriented in a series relationship with each other with respect to a common flow path, and optionally but preferably along a common axis. The common axis may be horizontal, vertical, or otherwise. During a regeneration step, reactants (e.g., fuel and oxygen) are permitted to combine or mix in a reaction zone to combust therein, in-situ, and create a high temperature zone or heat bubble inside a middle portion of the reactor system. The heat bubble can correspond to a temperature that is at least about the initial temperature for the endothermic reaction. Typically, the temperature of the heat bubble can be greater than the initial temperature for the endothermic reaction, as the temperature will decrease as heat is transferred from the heat bubble in a middle portion of the reactor toward the ends of the reactor. In some aspects, the combining can be enhanced by a reactant mixer that mixes the reactants to facilitate substantially complete combustion/reaction at the desired location, with the mixer optionally located between the first and second reactors. The combustion process can take place over a long enough duration that the flow of first and second reactants through the first reactor also serves to displace a substantial portion, (as desired) of the heat produced by the reaction (e.g., the heat bubble), into and at least partially through the second reactor, but preferably not all of the way through the second reactor to avoid waste of heat and overheating the second reactor. The flue gas may be exhausted through the second reactor, but preferably most of the heat is retained within the second reactor. The amount of heat displaced into the second reactor during the regeneration step can also be limited or determined by the desired exposure time or space velocity that the hydrocarbon feed gas will have in the endothermic reaction environment.

After regeneration or heating the second reactor media (such as a phase stable monolith as described herein), in the next/reverse step or cycle, reactants for the endothermic reaction methane (and/or natural gas and/or another hydrocarbon) can be supplied or flowed through the second reactor, from the direction opposite the direction of flow during the heating step. For example, in a reforming process, methane (and/or natural gas and/or another hydrocarbon) can be supplied or flowed through the second reactor. The methane can contact the hot second reactor and mixer media, in the heat bubble region, to transfer the heat to the methane for reaction energy.

For some aspects, the basic two-step asymmetric cycle of a reverse flow regenerative bed reactor system is depicted in FIGS. 1(a) and 1(b) of FIG. 1 in terms of a reactor system having two zones/reactors; a first or recuperator/quenching zone (7) and a second or reaction zone (1). Both the reaction zone (1) and the recuperator zone (7) can contain regenerative monoliths and/or other regenerative structures. Regenerative monoliths or other regenerative structures, as used herein, comprise materials that are effective in storing and transferring heat as well as being effective for carrying out a chemical reaction. The regenerative monoliths and/or other structures can correspond to any convenient type of material that is suitable for storing heat, transferring heat, and catalyzing a reaction. Examples of structures can include bedding or packing material, ceramic beads or spheres, ceramic honeycomb materials, ceramic tubes, extruded monoliths, and the like, provided they are competent to maintain integrity, functionality, and withstand long term exposure to temperatures in excess of 1200° C., or in excess of 1400° C., or in excess of 1600° C., which can allow for some operating margin.

To facilitate description of FIG. 1, the reactor is described herein with reference to a reforming reaction. It is understood that other convenient types of endothermic reactions can generally be performed using a reverse flow reactor, such as the reactor shown in FIG. 1.

As shown in FIG. 1(a) of FIG. 1, at the beginning of the “reaction” step of the cycle, a secondary end 5 of the reaction zone 1 (a.k.a. herein as the second reactor) can be at an elevated temperature as compared to the primary end 3 of the reaction zone 1, and at least a portion (including the first end 9) of the recuperator or quench zone 7 (a.k.a. herein as the first reactor), can be at a lower temperature than the reaction zone 1 to provide a quenching effect for the resulting product. In an aspect where the reactors are used to perform reverse flow reforming, a methane-containing reactant feed (or other hydrocarbon-containing reactant feed) can be introduced via a conduit(s) 15, into a primary end 3 of the reforming or reaction zone 1. In various aspects, the hydrocarbon-containing reactant feed can also contain H₂O, CO₂, or a combination thereof.

The feed stream from inlet(s) 15 can absorb heat from reaction zone 1 and endothermically react to produce the desired synthesis gas product. As this step proceeds, a shift in the temperature profile 2, as indicated by the arrow, can be created based on the heat transfer properties of the system. When the ceramic catalyst monolith/other catalyst structure is designed with adequate heat transfer capability, this profile can have a relatively sharp temperature gradient, which gradient can move across the reaction zone 1 as the reforming step proceeds. In some aspects, a sharper temperature gradient profile can provide for improved control over reaction conditions. In aspects where another type of endothermic reaction is performed, a similar shift in temperature profile can occur, so that a temperature gradient moves across reaction zone 1 as the reaction step proceeds.

The effluent from the reforming reaction, which can include unreacted feed components (hydrocarbons, H₂O, CO₂) as well as synthesis gas components, can exit the reaction zone 1 through a secondary end 5 at an elevated temperature and pass through the recuperator reactor 7, entering through a second end 11, and exiting at a first end 9. The recuperator 7 can initially be at a lower temperature than the reaction zone 1. As the products (and optionally unreacted feed) from the reforming reaction pass through the recuperator zone 7, the gas can be quenched or cooled to a temperature approaching the temperature of the recuperator zone substantially at the first end 9, which in some embodiments can be approximately the same temperature as the regeneration feed introduced via conduit 19 into the recuperator 7 during the second step of the cycle. As the reforming effluent is cooled in the recuperator zone 7, a temperature gradient 4 can be created in the zone's regenerative bed(s) and can move across the recuperator zone 7 during this step. The quenching can heat the recuperator 7, which can be cooled again in the second step to later provide another quenching service and to prevent the size and location of the heat bubble from growing progressively through the quench reactor 7. After quenching, the reaction gas can exit the recuperator at 9 via conduit 17 and can be processed for separation and recovery of the various components.

The second step of the cycle, referred to as the regeneration step, can then begin with reintroduction of the first and second regeneration reactants via conduit(s) 19. The first and second reactants can pass separately through hot recuperator 7 toward the second end 11 of the recuperator 7, where they can be combined for exothermic reaction or combustion in or near a central region 13 of the reactor system.

An example of the regeneration step is illustrated in FIG. 1(b) of FIG. 1. Regeneration can entail transferring recovered sensible heat from the recuperator zone 7 to the reaction zone 1 to thermally regenerate the reaction beds 1 for the subsequent reaction cycle. Regeneration gas/reactants can enter recuperator zone 7, such as via conduit(s) 19, and flow through the recuperator zone 7 and into the reaction zone 1. In doing so, the temperature gradients 6 and 8 may move across the beds as illustrated by the arrows on the exemplary graphs in FIG. 1(b), similar to but in opposite directions to the graphs of the temperature gradients developed during the reaction cycle in FIG. 1(a) of FIG. 1. Fuel and oxidant reactants may combust at a region proximate to the interface 13 of the recuperator zone 7 and the reaction zone 1. The heat recovered from the recuperator zone together with the heat of combustion can be transferred to the reaction zone, thermally regenerating the regenerative reaction monoliths and/or beds 1 disposed therein.

In some aspects, several of the conduits within a channel may convey a mixture of first and second reactants, due at least in part to some mixing at the first end (17) of the first reactor. However, the numbers of conduits conveying combustible mixtures of first and second reactants can be sufficiently low such that the majority of the stoichiometrically reactable reactants will not react until after exiting the second end of the first reactor. The axial location of initiation of combustion or exothermic reaction within those conduits conveying a mixture of reactants can be controlled by a combination of temperature, time, and fluid dynamics. Fuel and oxygen usually require a temperature-dependent and mixture-dependent autoignition time to combust. Still though, some reaction may occur within an axial portion of the conduits conveying a mixture of reactants. However, this reaction can be acceptable because the number of channels having such reaction can be sufficiently small that there is only an acceptable or inconsequential level of effect upon the overall heat balance within the reactor. The design details of a particular reactor system can be selected so as to avoid mixing of reactants within the conduits as much as reasonably possible.

FIG. 2 illustrates another exemplary reactor system that may be suitable in some applications for controlling and deferring the combustion of fuel and oxidant to achieve efficient regeneration heat. FIG. 2 depicts a single reactor system, operating in the regeneration cycle. The reactor system may be considered as comprising two reactor zones. The recuperator 27 can be the zone primarily where quenching takes place and provides substantially isolated flow paths or channels for transferring both of the quenching reaction gases through the reactor media, without incurring combustion until the gasses arrive proximate or within the reactor core 13 in FIG. 1. The reformer 2 can be the reactor where regeneration heating and methane (and/or hydrocarbon) reformation primarily occurs, and may be considered as the second reactor for purposes herein. Although the first and second reactors in the reactor system are identified as separately distinguishable reactors, it is understood that the first and second reactors may be manufactured, provided, or otherwise combined into a common single reactor bed, whereby the reactor system might be described as comprising merely a single reactor that integrates both cycles within the reactor. The terms “first reactor” and “second reactor” can merely refer to the respective zones within the reactor system whereby each of the regeneration, reformation, quenching, etc., steps take place and do not require that separate components be utilized for the two reactors. However, various aspects can comprise a reactor system whereby the recuperator reactor includes conduits and channels as described herein, and the reformer reactor may similarly possess conduits. Additionally or alternately, some aspects may include a reformer reactor bed that is arranged different from and may even include different materials from, the recuperator reactor bed.

As discussed previously, the first reactor or recuperator 27 can include various gas conduits 28 for separately channeling two or more gases following entry into a first end 29 of the recuperator 27 and through the regenerative bed(s) disposed therein. A first gas 30 can enter a first end of a plurality of flow conduits 28. In addition to providing a flow channel, the conduits 28 can also comprise effective flow barriers (e.g., which effectively function such as conduit walls) to prevent cross flow or mixing between the first and second reactants and maintain a majority of the reactants effectively separated from each other until mixing is permitted. As discussed previously, each of the first and second channels can comprise multiple channels or flow paths. The first reactor may also comprise multiple substantially parallel flow segments, each comprising segregated first and second channels.

In some aspects, the recuperator can be comprised of one or more extruded honeycomb monoliths, as described above. Each monolith may provide flow channel(s) (e.g., flow paths) for one of the first or second reactants. Each channel preferably includes a plurality of conduits. Alternatively, a monolith may comprise one or more channels for each reactant with one or more channels or groups of conduits dedicated to flowing one or more streams of a reactant, while the remaining portion of conduits flow one or more streams of the other reactant. It is recognized that at the interface between channels, a number of conduits may convey a mixture of first and second reactant, but this number of conduits is proportionately small.

Alternative embodiments may use reactor media other than monoliths, such as whereby the channel conduits/flow paths may include a more tortuous pathways (e.g. convoluted, complex, winding and/or twisted but not linear or tubular), including but not limited to labyrinthine, variegated flow paths, conduits, tubes, slots, and/or a pore structure having channels through a portion(s) of the reactor and may include barrier portion, such as along an outer surface of a segment or within sub-segments, having substantially no effective permeability to gases, and/or other means suitable for preventing cross flow between the reactant gases and maintaining the first and second reactant gases substantially separated from each other while axially transiting the recuperator 27. Such other types of reactor media can be suitable, so long as at least a portion of such media can be formed by sintering a ceramic catalytic composition as described herein, followed by exposing such media to reducing conditions to activate the catalyst. For such embodiments, the complex flow path may create a lengthened effective flow path, increased surface area, and improved heat transfer. Such design may be preferred for reactor embodiments having a relatively short axial length through the reactor. Axially longer reactor lengths may experience increased pressure drops through the reactor. However for such embodiments, the porous and/or permeable media may include, for example, at least one of a packed bed, an arrangement of tiles, a permeable solid media, a substantially honeycomb-type structure, a fibrous arrangement, and a mesh-type lattice structure.

In some aspects, the reverse flow reactor can include some type of equipment or method to direct a flow stream of one of the reactants into a selected portion of the conduits. In the exemplary embodiment of FIG. 2, a gas distributor 31 can direct a second gas stream 32 to second gas stream channels that are substantially isolated from or not in fluid communication with the first gas channels, here illustrated as channels 33. The result can be that at least a portion of gas stream 33 is kept separate from gas stream 30 during axial transit of the recuperator 27. In some aspects, the regenerative bed(s) and/or monolith(s) of the recuperator zone can comprise channels having a gas or fluid barrier that isolates the first reactant channels from the second reactant channels. Thereby, both of the at least two reactant gases that transit the channel means may fully transit the regenerative bed(s), to quench the regenerative bed, absorb heat into the reactant gases, before combining to react with each other in the combustion zone.

In various aspects, gases (including fluids) 30 and 32 can each comprise a component that reacts with a component in the other reactant 30 and 32, to produce an exothermic reaction when combined. For example, each of the first and second reactant may comprise one of a fuel gas and an oxidant gas that combust or burn when combined with the other of the fuel and oxidant. By keeping the reactants substantially separated, the location of the heat release that occurs due to exothermic reaction can be controlled. In some aspects “substantially separated” can be defined to mean that at least 50 percent, or at least 75 percent, or at least 90 percent of the reactant having the smallest or limiting stoichiometrically reactable amount of reactant, as between the first and second reactant streams, has not become consumed by reaction by the point at which these gases have completed their axial transit of the recuperator 27. In this manner, the majority of the first reactant 30 can be kept isolated from the majority of the second reactant 32, and the majority of the heat release from the reaction of combining reactants 30 and 32 can take place after the reactants begin exiting the recuperator 27. The reactants can be gases, but optionally some reactants may comprise a liquid, mixture, or vapor phase.

The percent reaction for these regeneration streams is meant the percent of reaction that is possible based on the stoichiometry of the overall feed. For example, if gas 30 comprised 100 volumes of air (80 volumes N₂ and 20 Volumes O₂), and gas 32 comprised 10 volumes of hydrogen, then the maximum stoichiometric reaction would be the combustion of 10 volumes of hydrogen (H₂) with 5 volumes of oxygen (O₂) to make 10 volumes of H₂O. In this case, if 10 volumes of hydrogen were actually combusted in the recuperator zone (27), this would represent 100% reaction of the regeneration stream. This is despite the presence of residual un-reacted oxygen, because in this example the un-reacted oxygen was present in amounts above the stoichiometric requirement. Thus, in this example the hydrogen is the stoichiometrically limiting component. Using this definition, less than 50% reaction, or less than 25% reaction, or less than 10% reaction of the regeneration streams can occur during the axial transit of the recuperator (27).

In various aspects, channels 28 and 33 can comprise ceramic (including zirconia), alumina, or other refractory material capable of withstanding temperatures exceeding 1200° C., or 1400° C., or 1600° C. Additionally or alternately, channels 28 and 33 can have a wetted area between 50 ft⁻¹ and 3000 ft⁻¹, or between 100 ft⁻¹ and 2500 ft⁻¹, or between 200 ft⁻¹ and 2000 ft⁻¹.

Referring again briefly to FIG. 1, the reactor system can includes a first reactor 7 containing a first end 9 and a second end 11, and a second reactor 1 containing a primary end 3 and a secondary end 5. The embodiments illustrated in FIGS. 1 and 2 are merely simple illustrations provided for explanatory purposes only and are not intended to represent a comprehensive embodiment. Reference made to an “end” of a reactor merely refers to a distal portion of the reactor with respect to an axial mid-point of the reactor. Thus, to say that a gas enters or exits an “end” of the reactor, such as end 9, means merely that the gas may enter or exit substantially at any of the various points along an axis between the respective end face of the reactor and a mid-point of the reactor, but more preferably closer to the end face than to the mid-point. Thereby, one or both of the first and second reactant gases could enter at the respective end face, while the other is supplied to that respective end of the reactor through slots or ports in the circumferential or perimeter outer surface on the respective end of the reactor.

EXAMPLES

In the Examples below, the monoliths used for supporting the catalyst systems corresponded to monoliths with 400 cpsi (cells per square inch) and an open frontal area of either 35% or 52%.

Example 1A—NiO/Al₂O₃(NiAl₂O₄)

α-Al₂O₃ powder was dried in an oven overnight at 121° C. (˜250° F.). The dried α-Al₂O₃ powder was then weighed, and mixed with the appropriate amount of NiO. This corresponded to a 1.5:1 Al:Ni mole ratio for the NiO/Al₂O₃ catalyst system. It is noted that this catalyst system can form NiAl₂O₄ in-situ after exposure to cyclic high temperature reforming conditions. The mixture was mixed in a Waring Blender. The blended material was then calcined at 1300° C. (˜2372° F.) in a Sentro Tech Furnace for 4 hours, using a ramp rate of 3° C./min, producing the desired NiO/Al₂O₃ catalyst system. The calcined material was allowed to cool to room temperature. The weight percent of catalytic metal (Ni) in the NiO/Al₂O₃ catalyst system was 38.8 wt % (relative to a weight of the catalyst system). The calcined NiO/Al₂O₃ catalyst system was further milled in a liquid to prepare appropriate slurry and washcoated on monoliths having 93 wt % α-Al₂O₃, 5 wt % SiO₂ and 2 wt % MgO. The washcoated monoliths were further calcined at 1200° C. (2192° F.) for 2 hours to ensure complete adherence of the active material onto the monoliths. This corresponded to annealing at a temperature that was substantially similar to the peak temperature during the subsequent exposure of the monoliths to cyclic high temperature reforming conditions. The final washcoated monoliths were loaded at the highest temperature catalytic zone (e.g. 800˜1250° C.) in a pilot scale reverse flow reactor unit and exposed to various cyclic process conditions for about 750 hours. FIG. 5 shows a scanning electron microscope (SEM) image of the NiO and NiAl₂O₄ materials that were present on the monoliths having 93 wt % α-Al₂O₃, 5 wt % SiO₂ and 2 wt % MgO after 750 hrs. During the exposure to the various cyclic process conditions, the NiAl₂O₄ catalyst system provided steady and high methane conversion, good phase stability of the metal oxide support, insignificant sintering of active catalytic metals, and good adhesion to the monoliths.

Examples 1B and 1C—NiAl₂O₄ and Al₂O₃/NiAl₂O₄

Additional catalyst systems and corresponding washcoated monoliths were prepared according to the method in Example 1A, but with varying ratios of NiO to Al₂O₃. In Example 1B, the initial Al:Ni ratio was 2:1, resulting in a catalyst system with an Ni content of roughly 33.2 wt % (relative to the weight of the catalyst system). This roughly corresponds to the stoichiometric ratio for NiAl₂O₄. The catalyst system with the 2:1 ratio of Al:Ni was then washcoated on to a monolith with the same type of washcoat composition as the monolith in Example 1A, using a similar procedure. For Example 1C, the initial Al:Ni ratio was 3:1, so that excess Al₂O₃ was present in the catalyst system. This resulted in forming a catalyst system with an Ni content of roughly 25.8 wt %. The catalyst system was then deposited as a washcoat on a monolith with the same type of washcoat composition as used in Examples 1A and 1B.

Example 2—Rh/α-Al₂O₃

In this example, the catalyst system corresponds to Rh (Rh₂O₃) as catalytic metal (oxide) and α-Al₂O₃ as the metal oxide support layer. α-Al₂O₃ corresponds to a “corundum” type oxide. To make this catalyst system, α-Al₂O₃ powder was dried in an oven overnight at 121° C. (˜250° F.). The dried α-Al₂O₃ was then weighed, and small aliquot was taken in order to determine the absorption factor. A solution of rhodium (III) nitrate, Rh(NO₃)₃.nH₂O, aqueous solution containing 9.77 wt % Rh at 27.4% solids content, was mixed with the appropriate amount of excess H₂O (as necessary), and sprayed/impregnated onto the α-Al₂O₃. The material was then dried at 121° C. (250° F.) for at least 2 hrs. The dried material was then calcined at 500° C. (932° F.) in a Sentro Tech Furnace for 4 hours, using a ramp rate of 3° C./min, producing Rh₂O₃/α-Al₂O₃. The calcined material was allowed to cool to room temperature. The weight percent of catalytic metal Rh was roughly 4.0 wt %. The calcined Rh₂O₃/α-Al₂O₃ catalyst system was further milled in a solution to prepare appropriate slurry and washcoated on monoliths having 93 wt % α-Al₂O₃, 5 wt % SiO₂ and 2 wt % MgO. The washcoated monoliths were further calcined at 500° C. (932° F.) for 2 hours to ensure complete adherence of the active material onto the monoliths. The final washcoated monoliths were loaded at the low temperature catalytic zone (e.g. 400˜1050° C.) in a pilot scale reverse flow reactor unit and exposed to various cyclic process conditions for about 750 hours. The desired Rh₂O₃/α-Al₂O₃ catalyst system had steady high methane conversion, good phase stability of the metal oxide support, reduced or minimized sintering of active catalytic metals, and good adhesion to the monolith. FIG. 6 shows scanning electron microscope (SEM) images of an example of the Rh₂O₃/α-Al₂O₃ catalyst system washcoated on a monolith having 93 wt % α-Al₂O₃, 5 wt % SiO₂ and 2 wt % MgO after 750 hrs.

Example 3—NiO/YSZ

In this example, the catalyst system corresponds to Ni (NiO) as the catalytic metal (oxide) and yttria stabilized zirconia (YSZ) as the metal oxide support layer (based on stabilized zirconia oxide). A catalyst system including 60 wt % NiO was prepared by mixing appropriate amounts of NiO powder and YSZ powder. An α-alumina slurry was washcoated on a monolith composed of 95 wt % α-Al₂O₃, 4 wt % SiO₂ and 1 wt % TiO₂. The washcoated monolith was sintered at 1450° C. for 2 hours to make an intermediate bond layer. The NiO/YSZ active material slurry was then washcoated on top of the intermediate bond layer and sintered at 1300° C. for 2 hours. The resulted in a structure that included three parts: i) NiO/YSZ active material, ii) α-Al₂O₃ intermediate bond layer, and iii) a monolith composed of 95 wt % α-Al₂O₃, 4 wt % SiO₂ and 1 wt % TiO₂. A scanning electron microscope (SEM) cross sectional image of the structure of the monolith with NiO/YSZ active material and intermediate bond layer is shown in FIG. 7.

Example 4—NiO/SLT

In this example, Ni (NiO) is the catalytic metal (oxide) and Sr_(0.65)La_(0.35)TiO₃ (SLT) is the metal oxide support layer of a catalyst system. The metal oxide support layer corresponds to a perovskite oxide. To form the catalyst system, a solution of nickel nitrate, Ni(NO₃)₂.6H₂O, was prepared and mixed with Sr_(0.65)La_(0.35)TiO₃ (SLT) powder. After calcination at 1300° C., a powder including 22 wt % NiO and 78 wt % Sr_(0.65)La_(0.35)TiO₃ (SLT) was prepared. The catalyst system powder was further milled in a solution to prepare a proper slurry for washcoating. The resulting washcoated monolith was composed of two parts: i) an NiO/SLT catalyst system, and ii) 95 wt % α-Al₂O₃, 4 wt % SiO₂ and 1 wt % TiO₂ monolith. The catalyst system was roughly 5 wt % of the total weight of the washcoated monolith.

Example 5—NiRh/Hibonite

In this prophetic example, the catalyst system corresponds to a binary alloy of Ni (NiO) and Rh (Rh₂O₃) as the catalyst (oxide) and hibonite, (Ca,Ce)(Al,Ti,Mg)₁₂O₁₉, as a metal oxide support based on hibonite oxide. To form the catalyst system, a mixed solution of nickel nitrate, Ni(NO₃)₂.6H₂O, and rhodium (III) nitrate, Rh(NO₃)₃.nH₂O, can be prepared with the appropriate amount of excess H₂O (as needed), and can be impregnated onto hibonite powder. After calcination at 1300° C., a catalyst system powder comprising 10 wt % NiO, 2 wt % Rh₂O₃, and 88 wt % hibonite, (Ca,Ce)(Al,Ti,Mg)₁₂O₁₉, can be formed. The catalyst system powder can be further milled in a solution to prepare a proper slurry for washcoating. The resulting washcoated monolith can be composed of two parts: i) NiRh/hibonite catalyst system, and ii) a monolith composed of 93 wt % α-Al₂O₃, 4 wt % SiO₂, 2 wt % MgO and 1 wt % Na₂O. The catalyst system can correspond to roughly 5 wt % of the total weight of the washcoated monolith.

Example 6—Rh₂O₃/USY

In this example, the catalyst system corresponds to Rh (Rh₂O₃) as a catalytic metal (oxide) and USY zeolite as a metal oxide support based on zeolite oxide. USY zeolite powder was dried in an oven overnight at 121° C. (250° F.). The dried USY zeolite was weighed, and small aliquot taken in order to determine the absorption factor. An aqueous solution of rhodium (III) nitrate, Rh(NO₃)₃.nH₂O, containing 9.77 wt % Rh at 27.4% solids content, was mixed with the appropriate amount of excess H₂O (as needed), and sprayed/impregnated onto the USY zeolite. The material was then dried at 121° C. (250° F.) for at least 2 hours, and weighed. The dried materials were then be calcined at 500° C. (932° F.) in a Sentro Tech Furnace for 4 hours, using a ramp rate of 3° C./min, producing a calcined powder of Rh on USY zeolite, with the Rh in the oxide form (Rh₂O₃). The calcined material was allowed to cool to room temperature. The weight percent of catalytic metal Rh in the Rh₂O₃/USY zeolite catalyst system was 1.5 wt %. The calcined Rh₂O₃/USY zeolite active material was further milled in a solution to prepare an appropriate slurry and washcoated on a monolith composed of 93 wt % α-Al₂O₃, 5 wt % SiO₂ and 2 wt % MgO. The washcoated monolith was further calcined at 500° C. (932° F.) for 2 hours to ensure adherence of the catalyst system onto the monolith. The resulting structure was composed of two parts: i) Rh₂O₃/USY zeolite catalyst system, and ii) 93 wt % α-Al₂O₃, 5 wt % SiO₂ and 2 wt % MgO monolith.

Examples 7A, 7B, and 7C—Catalyst Systems with Different Starting Alumina Phases

Three different types of catalyst system washcoat preparations were used to prepare multi-zone catalyst systems for hydrocarbon reforming. In this Example, a multi-zone catalyst system was used, with two catalyst zones. A first zone (higher temperature) corresponded to a Ni-containing catalyst, while a second zone (lower temperature) corresponded to a Rh-containing catalyst. Two monoliths were used to fill the desired catalyst bed volume in each zone in the pilot scale reactor, so each catalyst system corresponded to a total of four monoliths.

For Example 7A, the first two monoliths with the Ni-containing catalyst system was prepared according to Example 1A. Thus, the catalyst was NiO while the alumina phase in the first two monoliths in Example 7A was α-Al₂O₃. This type of catalyst system can result in in-situ formation of NiAl₂O₄ after exposure to cyclic high temperature reforming conditions. A sufficient washcoat was applied so that the weight of the NiO/α-Al₂O₃ catalyst system was roughly 5 wt % of the total weight of the washcoated monolith. For Example 7A, the second two monoliths with the Rh-containing catalyst system were prepared according to Example 2. Thus, the alumina phase in the second two monoliths in Example 7A was α-Al₂O₃. A sufficient washcoat was applied so that the weight of the Rh₂O₃/α-Al₂O₃ catalyst system was roughly 4 wt % of the total weight of the washcoated monolith.

For Examples 7B and 7C, instead of using catalyst systems comprised of phase stable materials, a washcoat containing higher surface-area material was deposited on a monolith. Thus, the washcoats used in Examples 7B and 7C did not include a thermally stable metal oxide support layer.

In Example 7B, the catalyst system for the first two washcoats corresponded to θ-Al₂O₃ doped with 4 wt % La, with 30% Ni as the catalyst, which was formed at 1200° C. This type of composition can be referred to as 30% Ni-4%-La-θ-Al₂O₃. This catalyst system corresponds to a molar ratio of Al:Ni of 3.7:1. It is noted that this ratio has a substantial amount of excess Al relative to the stoichiometric ratio for NiAl₂O₄. After depositing the washcoat, the first two monoliths in Example 7B were calcined at 500° C. For the second two monoliths in Example 7B, a washcoat of 5% Rh on 4%-La-γ-Al₂O₃ was washcoated onto an alumina rich monolith. It is noted that the second two washcoats included γ-Al₂O₃ rather than the θ-Al₂O₃ of the first two washcoats. After depositing the washcoat, the second two monoliths in Example 7B were calcined at 500° C.

In Example 7C, the first two washcoats and second two washcoats were prepared in a manner similar to Example 7B, but the calcination temperature of the first two monoliths was different. In Example 7C, a calcination temperature of 1200° C. was used after applying the washcoat (as compared to the 500° C. used for calcination in Example 7B).

Example 8—Reforming with Monoliths with Different Starting Alumina Phases

The washcoated monoliths described in Examples 7A, 7B, and 7C were used in a pilot scale reactor to investigate changes in catalytic activity over time and to determine the structural stability of the washcoated monoliths. The monoliths were used to perform steam reforming on a methane feed under cyclic high temperature conditions. The reaction conditions included a regeneration step and a reforming step. During the regeneration step, air was used to provide the source of oxygen for combustion of hydrocarbon fuel. The amount of air was sufficient to provide a 10% excess of O₂ relative to the amount of hydrocarbon fuel used for heating. The regeneration step during each cycle was performed for roughly 15 seconds at a pressure of 150 psig (˜1.0 MPa-g). The combustion during the regeneration step was performed to provide a temperature profile similar to the temperature profile shown in FIG. 4, but with a target peak temperature of 1150° C. at the end of the regeneration step/beginning of the reforming step. The reforming step during each cycle was performed for roughly 15 seconds at a pressure of 300 psig (˜2.1 MPa-g), with methane as the hydrocarbon for reforming. The molar ratio of H₂O to CH₄ in the reforming step feed was 1.3.

FIG. 7 shows the average conversion of methane during the reforming step (right plot) as the process is performed over a period of 4-6 weeks. Because of the impact of cooling in the reactor toward the end of a reforming step during a single cycle, the conversion rate at the end of the reforming step in each cycle is somewhat lower. This is illustrated by the difference in conversion when averaging over the first 10 seconds of each reforming step (left plot in FIG. 7) versus averaging over the first 15 seconds of each reforming step (right plot in FIG. 7). It is noted that a shorter reforming step could be used if it is desirable to maintain higher overall conversion for the full length of the reforming step.

As shown in the right plot in FIG. 7, both Example 7B and Example 7C initially provided higher conversion than Example 7A. This matches the expected effect of using the higher surface area phases of alumina as the support in Examples 7B and 7C. However, as shown in the right plot in FIG. 7, the activity for conversion of the catalysts in Examples 7B and 7C is not stable. While the data is noisy, it is clear that the conversion activity for the catalyst in Example 7C starts to decline almost immediately after start of run. This activity decline continues until about 300 hours of performing the cyclic reaction. At that point, the reaction in Example 7C was stopped due to the rapid loss of activity that was occurring. Example 7B has a more gradual decline in catalytic activity, but Example 7B also undergoes a substantial drop in activity that started well before 400 hours of time on service. Between 400 hours and 800 hours, an alternative set of cyclic reforming conditions were used that are not plotted in FIG. 7, but a similar drop in activity over time was observed. At 800 hours, the process conditions were restored to the initial reforming conditions. By 800 hours, the degradation of the catalyst appeared to stabilize, albeit at a significantly lower activity level than the catalyst of Example 7A. Again, this loss in activity is believed to be due to degradation of the catalyst system on the monolith in the reactor, resulting in loss of available surface area for the exposing the methane feed to the catalyst.

In contrast to Example 7B and Example 7C, the right plot in FIG. 7 shows that the catalyst system in Example 7A maintained similar activity throughout the full length of the process run. Without being bound by any particular theory, it is believed that this is due to Example 7A corresponding to a) monoliths made from a material that is phase stable under the cyclic high temperature reforming conditions and b) the monoliths including an oxide support layer, so that any interaction between a catalyst metal (such as Ni) and an oxide material (such as Al₂O₃) occurs in the oxide support layer, and does not impact the structural integrity of the underlying monolith or other support structure.

The left plot in FIG. 7 shows similar results. Again, Example 7C initially shows higher activity than Example 7A, but the activity for Example 7C started to decline almost immediately. Examples 7A and 7B initially had similar activity, but only Example 7A maintained that activity. As shown in both plots in FIG. 7, Example 7A maintained substantially the same activity for a run length of 750 hours.

In order to further characterize the results from performing cyclic reforming for the catalyst system and monolith from Example 7A, at the end of the run, alternating oxidation and reduction cycles were maintained while the peak temperature in the reactor was cooled to 1000° C. An N₂ flow was then used to cool the reactor down to room temperature. After cooling, additional characterization was then performed.

After cooling, it was initially noted that for the first and second monolith of Example 7A, the catalyst system was difficult to remove from the underlying monolith. Due to structural breakdown, it is typically relatively easy to separate a catalyst or catalyst system from a monolith when the catalyst or catalyst system does not include a thermally stable metal oxide. However, it was unexpectedly found that by using a thermally phase stable support metal oxide in the catalyst system, strong adhesion of the catalyst system to the monolith could be maintained after extended exposure to the cyclic high temperature reforming environment.

After removal, the catalyst system from Example 7A was characterized using X-ray diffraction (XRD). The XRD spectra indicated that all of the catalyst systems were in stable phases. For the first monolith, the catalyst system was primarily in a reduced state. This was indicated based on the presence of substantial peaks for Ni and α-Al₂O₃ while little NiAl₂O₄ was present. The catalyst system for the second monolith was more oxidized, with a mixture of Ni, NiO, α-Al₂O₃, and NiAl₂O₄ being present. The XRD spectra for the third and fourth monoliths were similar to each other, with both showing primarily Rh and α-Al₂O₃. Additional microscopic analysis and elemental analysis of the catalyst systems was consistent with the XRD spectra.

Example 9—Modification of Excess Oxygen in Regeneration Step

Prior to removing the catalyst system from the first two monoliths of Example 7A, SEM micrographs were obtained of the surface of the catalyst system on the monoliths. FIG. 8 is a representative image of the micrographs. As shown in Example 8, substantial sintering of the Ni on the surface of the monolith had occurred. It was noted in Example 8 that the first monolith was in a primarily reduced state, while the second monolith was in a partially reduced state.

Without being bound by any particular theory, it is believed that the sintering observed in FIG. 8 was due to incomplete oxidation of Ni metal during the regeneration step under the regeneration conditions for the process cycle used in Example 8. In Example 8, a 10% excess of O₂ was used relative to the stoichiometric amount for combustion (i.e., an excess molar amount of oxygen of 10%). Based on the total amount of Ni metal within the pilot scale reactor, it was calculated that a 10% excess molar amount of oxygen (relative to the stoichiometry for combustion) corresponded to roughly 40%-50% of the amount of oxygen that would be needed to convert all Ni within the reactor from Ni metal to NiO. Given the amount of hydrogen present within a reforming environment, it is believed that substantially all of the exposed Ni in the reactor was converted from NiO to Ni during the reforming step of the cycle, and then only a portion of the Ni metal was being converted back to NiO during the regeneration step.

To test this hypothesis, additional reactor runs were performed using a second group of monoliths that were substantially the same in composition as the monoliths from Example 7A. The second group of monoliths were used to perform methane reforming under two sets of process conditions. First, the second group of monoliths was used to perform methane reforming under the same conditions used in Example 8. This corresponded to having a molar amount of excess O₂ used during the regeneration step of roughly 10% relative to the stoichiometric amount for combustion. After characterizing the amount of conversion using the conditions in Example 8, the process cycle was changed so that the molar amount of excess O₂ was roughly 30% during the regeneration step.

During each process cycle, the temperature of the mid-point of the reactor was recorded along with the average methane conversion during the first 10 seconds. FIG. 9 shows the results from using 10% molar excess O₂ and 30% molar excess O₂ with the second group of monoliths. For comparison, similar data from Example 7A is also displayed in FIG. 9. As shown in FIG. 9, using 10% molar excess O₂ using the new monoliths resulted in substantially the same level of methane conversion, relative to the reactor mid-point temperature, as was observed in Example 7A. However, a substantial increase in conversion was observed when the amount of O₂ in the regeneration step was increased to a molar excess of 30%. It is noted that a molar excess of roughly 24% would have provided the minimum stoichiometric amount of O₂ needed to oxidize all Ni in the reactor from Ni metal to NiO (or equivalently NiAl₂O₄). As shown in FIG. 19, using a sufficient molar excess of O₂ to fully oxidize all Ni in the reactor resulted in a substantial activity improvement.

Additionally, after obtaining the micrograph shown in FIG. 8, the first two monoliths from Example 7A were calcined in an O₂ environment at 1300° C. for four hours. SEM micrographs were obtained of the calcined monoliths. The additional micrographs indicated that re-dispersion of Ni had occurred, consistent with the results shown in FIG. 9.

Example 10—Ni/YSZ on Monolith Composed of NiAl₂O₄

An additional test run was performed in the pilot scale reactor where the first two monoliths were composed of NiAl₂O₄. For the first two monoliths, an intermediate bonding layer of Al₂O₃ was provided on the NiAl₂O₄ monoliths, followed by a Ni/YSZ catalyst system. The catalyst system washcoat corresponded to roughly 5 wt % of the total weight of the combined catalyst system and monolith. The third and fourth monoliths were similar to the third and fourth monoliths from Example 7A. Thus, the third and fourth monoliths included a washcoat of a Rh/α-Al₂O₃ catalyst system on a monolith composed of α-Al₂O₃.

The monoliths were then exposed to cyclic high temperature reforming conditions similar to those for Example 8. FIG. 10 shows the methane conversion during the course of the text run. As shown in FIG. 10, the catalytic activity was initially good, indicating that Ni/YSZ in combination with Rh/α-Al₂O₃ can be used effectively in multiple zones to achieve desirable reforming activity. However, after roughly 200 hours of exposure, the reforming activity dropped substantially. This is believed to be due to collapse of the first and second monoliths. The collapse of the first and second monoliths was visually confirmed after the test run was finished. Without being bound by any particular theory, it is believed that the cyclic oxidation and reduction environment caused rapid conversion of the underlying NiAl₂O₄ monolith between states of NiAl₂O₄ and (Ni+Al₂O₃). This cycling between states is believed to cause the structural breakdown of the monolith. Thus, although NiAl₂O₄ can potentially be used to construct a monolith, the benefits of using NiAl₂O₄ for reforming in a cyclic high temperature reforming environment cannot be realized over extended run lengths when NiAl₂O₄ is used as a monolith material. Instead, as shown in Example 8, using NiAl₂O₄ (preferably in the form NiO/NiAl₂O₄) as a catalyst system deposited on a phase stable monolith provides unexpectedly superior structural stability.

It is noted that even after the collapse of monoliths 1 and 2, substantial conversion of methane was still performed. This is believed to be due to the reforming activity provided by the Rh/α-Al₂O₃ catalyst system on the α-Al₂O₃ monoliths used for monoliths 3 and 4.

Additional Embodiments

Embodiment 1. A hydrocarbon reforming catalyst system and support structure, comprising: a support structure; a catalyst having reforming activity; and a metal oxide support layer that is thermally phase stable at 800° C. to 1600° C. comprising stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, a corundum group oxide, or a combination thereof, the catalyst and the metal oxide support layer comprising a catalyst system supported by one or more surfaces of the support structure, the catalyst system comprising 0.5 wt % or more of a combined weight of the catalyst system and the support structure.

Embodiment 2. A method for forming a catalyst system, comprising: forming a catalyst system comprising a catalyst and a metal oxide support layer that is thermally phase stable at 800° C. to 1600° C., the catalyst having reforming activity and comprising Ni, Rh, Ru, Pd, Pt, Cu, Ir, or a combination thereof, the metal oxide support layer comprising stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, a corundum group oxide, or a combination thereof; supporting the catalyst system on one or more surfaces of a support structure; annealing the supported catalyst system and the support structure at an annealing temperature of 1000° C. or more to form an annealed catalyst system and support structure; and exposing the annealed catalyst system and support structure to cyclic reforming conditions comprising a peak temperature of 1000° C. or more in the presence of a hydrocarbon feed to form H₂, the cyclic reforming conditions comprising a reforming step and a regeneration step, the annealing temperature optionally being greater than the peak temperature.

Embodiment 3. The method of Embodiment 2, wherein the regeneration step comprises a molar excess of O₂, relative to a stoichiometric amount of O₂ for combustion of fuel during the regeneration step, of 20% or more.

Embodiment 4. The method of Embodiment 2 or 3, wherein the catalyst system comprises a washcoat supported on the one or more surfaces of the support structure.

Embodiment 5. A method for reforming hydrocarbons in a cyclic reaction environment, comprising: reacting a mixture comprising fuel and 0.1 vol % or more of O₂ under combustion conditions in a combustion zone within a reactor to heat one or more surfaces in a reaction zone to a regenerated surface temperature of 1000° C. or more, the 0.1 vol % or more of O₂ comprising 120% or more of a stoichiometric molar amount of O₂ for combustion of the fuel, the reaction zone comprising a catalyst system supported on one or more surfaces of a support structure; exposing a reactant stream comprising a reformable hydrocarbon to the one or more surfaces in the reaction zone to increase the temperature of the reactant stream; and exposing the reactant stream to the catalyst system in the reaction zone at a temperature of 1000° C. or more to form a product stream comprising H₂, a direction of flow for the reactant stream within the reaction zone being reversed relative to a direction of flow for the mixture, wherein the catalyst system comprises a catalyst and a metal oxide support layer, the catalyst having reforming activity and comprising Ni, Rh, Ru, Pd, Pt, Cu, Ir, or a combination thereof, the metal oxide support layer comprising stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, a corundum group oxide, or a combination thereof, the metal oxide support layer optionally being thermally phase stable at 800° C. to 1600° C.

Embodiment 6. The method of Embodiment 5, wherein the 0.1 vol % or more of O₂ comprises 125% to 200% of a stoichiometric molar amount of O₂ for combustion of the fuel.

Embodiment 7. The method of any of Embodiments 2 to 6, wherein the metal oxide support layer comprises one or more metal oxides, and wherein forming the catalyst system comprises mixing a powder comprising the catalyst with a powder comprising the one or more metal oxides of the metal oxide support layer, the powder comprising the one or more metal oxides of the metal oxide support layer having a surface area of 20 m²/g or less.

Embodiment 8. The catalyst system and support structure or method of any of the above embodiments, wherein the catalyst system comprises NiAl₂O₄.

Embodiment 9. The catalyst system and support structure or method of any of the above embodiments, wherein a) the catalyst comprises an Ni-containing catalyst; b) the metal oxide support layer comprises α-Al₂O₃, yttria-stabilized zirconia (YSZ), a perovskite, or a combination thereof; c) the metal oxide support layer comprises 80 wt % or more α-Al₂O₃ relative to a weight of the support layer; or d) a combination of two or more of a), b) and c).

Embodiment 10. The catalyst system and support structure or method of Embodiment 9, wherein the Ni-containing catalyst further comprises Rh, Ru, Pd, Pt, Cu, Ir, Co, or a combination thereof.

Embodiment 11. The catalyst system and support structure or method of any of the above embodiments, wherein at least a portion of the catalyst system comprises a mixture of the catalyst and the metal oxide support layer.

Embodiment 12. The catalyst system and support structure or method of any of the above embodiments, further comprising an intermediate bonding layer comprising a metal oxide, a first surface of the intermediate bonding layer being in contact with at least a portion of the one or more surfaces of the support structure, the catalyst system being supported on the surface of the support structure by being supported at least in part on a second surface of the intermediate bonding layer, the intermediate bonding layer optionally comprising α-Al₂O₃.

Embodiment 13. The catalyst system and support structure or method of any of the above embodiments, further comprising a second catalyst zone comprising a second catalyst system, the second catalyst system comprising a second catalyst comprising Ni, Rh, Ru, Pd, Pt, Cu, Ir, or a combination thereof, the second catalyst optionally being Rh, the second catalyst system optionally further comprising a second metal oxide support layer that is thermally phase stable at 800° C. to 1600° C.

Embodiment 14. The catalyst system and support structure or method of any of the above embodiments, wherein the support structure comprises a monolith having a cell density of 50 cells per square inch to 900 cells per square inch, or wherein the support structure comprises 80 wt % or more of Al₂O₃, or a combination thereof.

Embodiment 15. The catalyst system and support structure or method of any of the above embodiments, wherein the catalyst system comprises 1.0 wt % to 10 wt % of the combined weight of the catalyst system and support structure; or wherein 80 wt % or more of the catalyst system remains adhered to the support structure after performing a mechanical attrition test; or a combination thereof.

Additional Embodiment A. Use of a catalyst system according to any of Embodiments 1-15 for reforming of hydrocarbons.

Additional Embodiment B. A method for reforming hydrocarbons in a cyclic reaction environment, comprising: reacting a mixture comprising fuel and 0.1 vol % or more of O₂ under combustion conditions in a combustion zone within a reactor to heat one or more surfaces in a reaction zone to a regenerated surface temperature of 800° C. or more, the reaction zone comprising a catalyst system supported on one or more surfaces of a support structure; exposing a reactant stream comprising a reformable hydrocarbon to the one or more surfaces in the reaction zone to increase the temperature of the reactant stream; and exposing the reactant stream to the catalyst system in the reaction zone at a temperature of 800° C. or more to form a product stream comprising H₂, a direction of flow for the reactant stream within the reaction zone being reversed relative to a direction of flow for the mixture, wherein the catalyst system comprises a catalyst and a metal oxide support layer, the catalyst having reforming activity and comprising Ni, Rh, Ru, Pd, Pt, Cu, Ir, or a combination thereof, the metal oxide support layer being thermally phase stable at 800° C. to 1600° C. and comprising stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, a corundum group oxide, or a combination thereof, the catalyst system comprising 0.5 wt % or more of a combined weight of the catalyst system and the support structure, the catalyst system and the support structure optionally comprising a catalyst system and support structure according to any of Embodiments 1-15.

While the present invention has been described and illustrated by reference to particular embodiments, those of ordinary skill in the art will appreciate that the invention lends itself to variations not necessarily illustrated herein. For this reason, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention. 

1. A hydrocarbon reforming catalyst system and support structure, comprising: a support structure; a catalyst having reforming activity; and a metal oxide support layer that is thermally phase stable at 800° C. to 1600° C. comprising stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, a corundum group oxide, or a combination thereof, the catalyst and the support layer comprising a catalyst system supported by one or more surfaces of the support structure, the catalyst system comprising 0.5 wt % or more of a combined weight of the catalyst system and the support structure.
 2. The catalyst system and support structure of claim 1, wherein the catalyst system comprises NiAl₂O₄.
 3. The catalyst system and support structure of claim 1, wherein the catalyst comprises an Ni-containing catalyst.
 4. The catalyst system and support structure of claim 3, wherein the metal oxide support layer comprises α-Al₂O₃, yttria-stabilized zirconia (YSZ), a perovskite, or a combination thereof.
 5. The catalyst system and support structure of claim 4, wherein the metal oxide support layer comprises 80 wt % or more α-Al₂O₃ relative to a weight of the metal oxide support layer.
 6. The catalyst system and support structure of claim 3, wherein the Ni-containing catalyst further comprises Rh, Ru, Pd, Pt, Cu, Ir, Co, or a combination thereof.
 7. The catalyst system and support structure of claim 1, wherein at least a portion of the catalyst system comprises a mixture of the catalyst and the metal oxide support layer.
 8. The catalyst system and support structure of claim 1, further comprising an intermediate bonding layer comprising a metal oxide, a first surface of the intermediate bonding layer being in contact with at least a portion of the one or more surfaces of the support structure, the catalyst system being supported on the surface of the support structure by being supported at least in part on a second surface of the intermediate bonding layer.
 9. The catalyst system and support structure of claim 8, wherein the intermediate bonding layer comprises α-Al₂O₃.
 10. The catalyst system and support structure of claim 1, further comprising a second catalyst zone comprising a second catalyst system, the second catalyst system comprising a second catalyst comprising Ni, Rh, Ru, Pd, Pt, Cu, Ir, or a combination thereof, the second catalyst system comprising a second metal oxide support layer that is thermally phase stable at 800° C. to 1600° C.
 11. The catalyst system and support structure of claim 10, wherein the second catalyst comprises Rh.
 12. The catalyst system and support structure of claim 1, wherein the support structure comprises a monolith having a cell density of 50 cells per square inch to 900 cells per square inch, or wherein the support structure comprises 80 wt % or more of Al₂O₃, or a combination thereof.
 13. The catalyst system and support structure of claim 1, wherein the catalyst system comprises 1.0 wt % to 10 wt % of the combined weight of the catalyst system and support structure.
 14. The catalyst system and support structure of claim 1, wherein 80 wt % or more of the catalyst system remains adhered to the support structure after performing a mechanical attrition test.
 15. A multi-zone reforming catalyst, comprising: a first support structure; a first Ni-containing catalyst having reforming activity; a first metal oxide support layer that is thermally phase stable at 800° C. to 1600° C. comprising stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, a corundum group oxide, or a combination thereof, the first catalyst and the first metal oxide support layer comprising a first catalyst system supported by one or more surfaces of the first support structure, the first catalyst system comprising 0.5 wt % or more of a combined weight of the first catalyst system and the first support structure; a second support structure; a second catalyst having reforming activity comprising Ni, Rh, Ru, Pd, Pt, Cu, Ir, or a combination thereof; and a second metal oxide support layer comprising stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, a corundum group oxide, or a combination thereof, the second catalyst and the second metal oxide support layer comprising a second catalyst system, the second catalyst system being different than the first catalyst system, the second catalyst system being supported by one or more surfaces of the second support structure.
 16. The multi-zone reforming catalyst of claim 15, wherein the second metal oxide support layer is thermally phase stable at 800° C. to 1600° C.
 17. The multi-zone reforming catalyst of claim 16, wherein the first catalyst comprises an Ni-containing catalyst and the second catalyst comprises an Rh-containing catalyst.
 18. A method for forming a catalyst system, comprising: forming a catalyst system comprising a catalyst and a metal oxide support layer that is thermally phase stable at 800° C. to 1600° C., the catalyst having reforming activity and comprising Ni, Rh, Ru, Pd, Pt, Cu, Ir, or a combination thereof, the metal oxide support layer comprising stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, a corundum group oxide, or a combination thereof; supporting the catalyst system on one or more surfaces of a support structure; annealing the supported catalyst system and the support structure at an annealing temperature of 1000° C. or more to form an annealed catalyst system and support structure; and exposing the annealed catalyst system and support structure to cyclic reforming conditions comprising a peak temperature of 1000° C. or more in the presence of a hydrocarbon feed to form H₂, the cyclic reforming conditions comprising a reforming step and a regeneration step.
 19. The method of claim 18, wherein supporting the catalyst system on one or more surfaces of the support structure comprises: forming a washcoat suspension comprising the catalyst system; and exposing the one or more surfaces of the support structure to the washcoat suspension to support the catalyst system on the one or more surfaces of the support structure.
 20. The method of claim 18, wherein the metal oxide support layer comprises one or more metal oxides, and wherein forming the catalyst system comprises mixing a powder comprising the catalyst with a powder comprising the one or more metal oxides of the metal oxide support layer, the powder comprising the one or more metal oxides of the metal oxide support layer having a surface area of 20 m²/g or less.
 21. The method of claim 18, wherein supporting the catalyst system on a surface of the metal oxide support structure comprises: depositing an intermediate bonding layer on at least a portion of the one or more surfaces of the support structure; and supporting at least a portion of the catalyst system on the intermediate bonding layer.
 22. The method of claim 18, wherein the annealing temperature is greater than the peak temperature.
 23. The method of claim 18, wherein the catalyst system comprises NiAl₂O₄.
 24. The method of claim 18, i) wherein the catalyst comprises an Ni-containing catalyst; ii) wherein the metal oxide support layer comprises α-Al₂O₃, yttria-stabilized zirconia (YSZ), a perovskite, or a combination thereof; or iii) a combination of i) and ii).
 25. A method for reforming hydrocarbons in a cyclic reaction environment, comprising: reacting a mixture comprising fuel and 0.1 vol % or more of O₂ under combustion conditions in a combustion zone within a reactor to heat one or more surfaces in a reaction zone to a regenerated surface temperature of 800° C. or more, the reaction zone comprising a catalyst system supported on one or more surfaces of a support structure; exposing a reactant stream comprising a reformable hydrocarbon to the one or more surfaces in the reaction zone to increase the temperature of the reactant stream; and exposing the reactant stream to the catalyst system in the reaction zone at a temperature of 800° C. or more to form a product stream comprising H₂, a direction of flow for the reactant stream within the reaction zone being reversed relative to a direction of flow for the mixture, wherein the catalyst system comprises a catalyst and a metal oxide support layer, the catalyst having reforming activity and comprising Ni, Rh, Ru, Pd, Pt, Cu, Ir, or a combination thereof, the metal oxide support layer being thermally phase stable at 800° C. to 1600° C. and comprising stabilized zirconia, perovskite, pyrochlore, spinel, hibonite, zeolite, a corundum group oxide, or a combination thereof, the catalyst system comprising 0.5 wt % or more of a combined weight of the catalyst system and the support structure. 